Water temperature as a means of controlling kinetics of onsite generated peracids

ABSTRACT

Methods and systems for temperature-controlled, on-site generation of peracids, namely peroxycarboxylic acids and peroxycarboxylic acid forming compositions are disclosed. In particular, methods for using an adjustable biocide formulator or generator system overcome the limitations of temperature on the kinetics of the peracid generation and/or peracid decomposition inside an adjustable biocide formulator or generator system. The methods include the controlling of the temperature of at least one raw starting material, namely water, to improve upon methods of on-site generation of peracids. The methods allow for the generation of user-selected chemistry without regard to the ambient temperatures of the raw starting materials and/or the biocide formulator or generator system.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/933,161, filed Mar. 22, 2018, which is a divisional of U.S. patentapplication Ser. No. 14/562,960, filed Dec. 8, 2014 (now U.S. Pat. No.10,010,075, issued Jul. 3, 2018), which is a divisional of U.S. patentapplication Ser. No. 13/331,385, filed Dec. 20, 2011 (now U.S. Pat. No.8,933,263, issued January 13, 2015), which claims priority to U.S.provisional application Ser. No. 61/427,951, entitled Sugar EsterPeracid On-Site Generator and Formulator, filed Dec. 29, 2010. Theentire contents of these patent applications are hereby expresslyincorporated herein by reference including, without limitation, thespecification, claims, and abstract, as well as any figures, tables, ordrawings thereof.

This application is related to U.S. patent application Ser. No.13/331,304, now issued U.S. Pat. No. 8,846,107, and Ser. No. 13/331,486,entitled In Situ Generation of Peroxycarboxylic Acids at Alkaline pH andMethods of Use Thereof, U.S. patent application Ser. No. 13/330,915,entitled Sugar Ester Peracid On-Site Generator and Formulator, U.S.patent application Ser. No. 13/331,104, now issued U.S. Pat. No.8,729,296, entitled Generation of Peroxycarboxylic Acids at Alkaline pH,and Their Use as Textile Bleaching and Antimicrobial Agents, U.S. patentapplication Ser. No. 13/330,981, now issued U.S. Pat. No. 8,858,895,entitled Continuous On-Line Adjustable Disinfectant/Sanitizer/BleachGenerator. The entire contents of these patent applications are herebyexpressly incorporated herein by reference including, withoutlimitation, the specification, claims, and abstract, as well as anyfigures, tables, or drawings thereof.

FIELD OF THE INVENTION

The invention relates to methods and systems for temperature-controlledon-site generation of peracids, namely peroxycarboxylic acids andperoxycarboxylic acid forming compositions for use as oxidizing agents.In particular, methods for using an adjustable biocide formulator orgenerator system are provided for on-site generation of peroxycarboxylicacids and peroxycarboxylic acid forming compositions from at least onesugar ester. Methods of use overcome the limitations of temperature onthe kinetics of the peracid generation. In particular, the presentinvention overcomes the limitation of temperature on the kinetics ofboth peracid production as well as the kinetics of peracid decompositioninside an adjustable biocide formulator or generator system.

BACKGROUND OF THE INVENTION

Peracids, also known as peroxyacids, are known for use as sanitizers,disinfectants, deodorizers, and bleaching agents, among other uses.Peroxycarboxylic acids in particular are known for use as antimicrobialsand bleaching agents. Peracids such as peroxycarboxylic acid have knownchemical disadvantages, namely, they are relatively instable in solutionand decompose to ordinary oxyacids and oxygen. Conventionalperoxycarboxylic acid compositions are made through an acid catalyzedequilibrium reaction. Most often, the peroxycarboxylic acids aregenerated in a chemical plant, and then shipped to customers for on-siteuse. Due to the limited storage stability of peroxycarboxylic acids theyare often packed in special containers and shipped under the strictDepartment of Transportation (DOT) guidelines. Certain improvements toperoxycarboxylic acid stability have proved advantageous for shippingpurposes, as described in U.S. patent application Ser. No. 11/847,604,entitled “Shelf Stable, Reduced Corrosion, Ready to Use PeroxycarboxylicAcid Antimicrobial Compositions,” the entire contents of which arehereby expressly incorporated herein by reference.

Most commercially available products in an equilibrium mixture containexcess hydrogen peroxide in the presence of stabilizers and acidcatalysts, to stabilize and improve the composition's shelf life.Despite such stability improvements, excess amounts of reagents (e.g.,acids, oxidizing agents, and stabilizers) must be present in thecompositions during shipping to prevent decomposition. Peroxycarboxylicacid instability, specifically limited storage stability, is describedin detail in U.S. Pat. No. 8,858,895, entitled “Enhanced StabilityPeracid Compositions,” the entire contents of which are hereby expresslyincorporated herein by reference.

Peracid generation is limited according to various kinetic reactions,including the temperature of the reaction. As a result, the generationof a peracid chemistry using the conventional acid catalyzed equilibriumreactions presents additional difficulties. In particular, changes inthe ambient temperature of a location of a generator and/or of a rawstarting material are expected to negatively impact the generation ofperacid chemistry.

Accordingly, it is an objective of the claimed invention to developmethods and systems for on-site generation of peracids, includingperoxycarboxylic acid generating compositions and peroxycarboxylic acidsthat are temperature insensitive.

A further object of the invention is to develop a system for generationof individual or mixed peracid chemistries according to user-orsystem-specific needs that may be generated in any on-site locationregardless of ambient temperature conditions.

BRIEF SUMMARY OF THE INVENTION

An advantage of the invention is a system and methods for on-sitegeneration of a biocide or antimicrobial agent. The system may beformulated into a number of designs, including for example, a mobilecart or generator that is particularly suitable for the on-sitegeneration of peracid chemistries required in batch formulations and/orcontinuously generated formulations. It is a particular advantage of thepresent invention that peracid chemistries, including peroxycarboxylicacid forming compositions or peroxycarboxylic acids are generatedon-site according to particular needs of a user or system to providedesired performance against particular organisms, as well as providingdesired volumes of the same chemistry. In addition, the on-sitegeneration is insensitive to the ambient temperatures of both thelocation of the system and the reagents utilized within the system.These benefits of the present invention ensure consistent generation ofthe peracid chemistries.

In an embodiment, the present invention is a method for on-site,temperature controlled peroxycarboxylic acid forming compositiongeneration or peroxycarboxylic acid generation comprising: inputting auser-desired or system-controlled peroxycarboxylic acid formingcomposition or peroxycarboxylic acid formulation into a control softwarefor on-site generation, wherein said input formulation selects anindividual or mixed peroxycarboxylic acid forming composition orperoxycarboxylic acid and corresponding volume or mass for on-sitegeneration; and combining one or more sugar esters of a polyhydricalcohol and a C1 to C18 carboxylic acid, a source of alkalinity and anoxidizing agent at alkaline pH in an adjustable biocide formulator orgenerator system at a pH above at least 12, wherein said system is anapparatus that is insensitive to environmental temperatures of thelocation of the apparatus and/or reagents comprising a reaction vessel,a series of feed pumps, an outlet for dosing a peroxycarboxylic acidforming composition from said reaction vessel and a controller for auser- or system-inputted selection device; and generating aperoxycarboxylic acid forming composition or peroxycarboxylic acidformulation; wherein said temperature insensitivity to the environmentaltemperatures of the location of the apparatus and/or reagents iscontrolled by a mechanism for maintaining a controlled temperature ofsaid reaction vessel and/or one or more reagents; wherein said feedpumps are in fluid connection with said reaction vessel and supply oneor more reagents to produce said peroxycarboxylic acid formingcomposition in said reaction vessel; and wherein said reaction vessel isin fluid connection with said outlet to dispense said peroxycarboxylicacid forming composition.

In a further embodiment, the present invention is a temperaturecontrolled adjustable biocide formulator or generator system for on-siteperoxycarboxylic acid forming composition generation comprising: anapparatus for producing peroxycarboxylic acid forming composition thatis insensitive to environmental temperatures of the location of theapparatus and/or reagents comprising a reaction vessel, a series of feedpumps, an outlet for dosing a peroxycarboxylic acid forming compositionfrom said reaction vessel and a controller for a user- orsystem-inputted selection device; a temperature controlled mechanism formaintaining a controlled temperature of said reaction vessel and/or oneor more reagents, wherein said reagents comprise an ester of apolyhydric alcohol and a C1 to C18 carboxylic acid, a source ofalkalinity and an oxidizing agent; wherein said feed pumps are in fluidconnection with said reaction vessel and supply one or more reagents toproduce said peroxycarboxylic acid forming composition in said reactionvessel; and wherein said reaction vessel is in fluid connection withsaid outlet to dispense said peroxycarboxylic acid forming composition.

In a still further embodiment, the present invention is a method ofcleaning using an on-site generated peroxycarboxylic acid formingcomposition comprising: obtaining a user- or system-inputtedperoxycarboxylic acid forming composition on-site using the adjustablebiocide formulator or generator system of claim 11; and applying saidperoxycarboxylic acid forming composition in an amount sufficient tosanitize, bleach or disinfect a surface in need thereof, wherein saidcomposition retains within about 10% of its final concentration ofperacid for at least about 1 minute, at least about 2 minutes, at leastabout 3 minutes, at least about 4 minutes, at least about 5 minutes,preferably within at least about 5-10 minutes, and more preferably formore than at least 10 minutes.

According to a preferred embodiment of the invention, the source ofalkalinity is sodium hydroxide (e.g. caustic soda), and the sodiumhydroxide is provided to said reaction vessel prior to the addition ofsaid ester in a solution that is less than about 20 wt-% sodiumhydroxide on an actives basis. Still further, the reaction goes tocompletion within less than about 30 minutes and the compositionmaintains a peracid concentration within about 10% of its finalcompletion concentration for at least about 1 minute.

According to various preferred embodiments of the invention, thetemperature control mechanism is selected from the group consisting ofexternal heating or cooling of the reaction vessel, internal heating ofthe reagents within the reaction vessel, preheating one or more of thereagents, and combinations of the same. The embodiments of the inventionmay utilize a reaction vessel is a flow through reactor (e.g. continuousgeneration) or a batch reactor and the heated reagent is water. Stillfurther, the composition may be neutralization with an acid or aqueousacidic solution when the concentration of peracid is within about 10% ofits final concentration. More preferably, the composition is dispensedfor use in a cleaning process when the concentration of peracid iswithin about 10% of its final concentration.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic diagram of a user or controller operatedcontinuous adjustable biocide formulator apparatus according to theinvention.

FIGS. 2A-2B show diagrams of an embodiment of an adjustable biocideformulator apparatus according to the invention, including descriptionof the dosing of raw starting materials (e.g. reagents) for thegeneration of peracid chemistries according to the invention.

FIG. 3 shows a graph representing POOA concentration over time atvarious reaction temperatures according to various embodiments of theadjustable biocide formulator apparatus according to the invention.

FIG. 4 shows a graph representing POOA production using the adjustablebiocide formulator apparatus according to the invention at varioustemperatures over a period of time.

FIG. 5 shows a graph representing POOA production and temperature as afunction of time according to various embodiments of the invention.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure relates to adjustable biocide formulator orgenerator systems for on-site peracid generation, including for exampleperoxycarboxylic acid forming compositions or peroxycarboxylic acids, aswell as methods of making and using such compositions. The compositionsand systems for making the compositions disclosed herein havesignificant advantages over conventional systems and methods for makingperoxycarboxylic acids or peroxycarboxylic acid forming compositions.For example, the systems allow on-site, user- or system-controlledformulation, eliminating the step of shipping hazardous peroxycarboxylicacid compositions to an end user. In addition, there are variousadvantages of the compositions, including having significantly lowerlevels of reactants, increased stability and ability to be generated insitu.

The embodiments of this invention are not limited to particular methodsand systems for on-site generation of sugar ester peracids for use asbiocides, which can vary and are understood by skilled artisans. It isfurther to be understood that all terminology used herein is for thepurpose of describing particular embodiments only, and is not intendedto be limiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form. Numeric ranges recited within the specificationare inclusive of the numbers defining the range and include each integerwithin the defined range.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

As used herein, “agricultural” or “veterinary” objects or surfacesinclude animal feeds, animal watering stations and enclosures, animalquarters, animal veterinarian clinics (e.g. surgical or treatmentareas), animal surgical areas, and the like. As used herein, the phrase“air streams” includes food anti-spoilage air circulation systems. Airstreams also include air streams typically encountered in hospital,surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms.

The term “cleaning,” as used herein, means to perform or aid in soilremoval, bleaching, microbial population reduction, or combinationthereof.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food processing, preparation, or storageactivity. Examples of food processing surfaces include surfaces of foodprocessing or preparation equipment (e.g., slicing, canning, ortransport equipment, including flumes), of food processing wares (e.g.,utensils, dishware, wash ware, and bar glasses), and of floors, walls,or fixtures of structures in which food processing occurs. Foodprocessing surfaces are found and employed in food anti-spoilage aircirculation systems, aseptic packaging sanitizing, food refrigerationand cooler cleaners and sanitizers, ware washing sanitizing, blanchercleaning and sanitizing, food packaging materials, cutting boardadditives, third-sink sanitizing, beverage chillers and warmers, meatchilling or scalding waters, auto dish sanitizers, sanitizing gels,cooling towers, food processing antimicrobial garment sprays, andnon-to-low-aqueous food preparation lubricants, oils, and rinseadditives.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat (e.g., red meat and pork), seafood, poultry, produce (e.g.,fruits and vegetables), eggs, living eggs, egg products, ready to eatfood, wheat, seeds, roots, tubers, leafs, stems, corns, flowers,sprouts, seasonings, or a combination thereof. The term “produce” refersto food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

As used herein, the term “fouling” shall be understood to mean theundesirable presence of or any deposition of any organic or inorganicmaterial in the applicable composition or chemistry.

As used herein, the term “free” or “substantially free” refers to acomposition, mixture, or ingredient that does not contain a particularcompound or to which a particular compound or a particularcompound-containing compound has not been added. Should the particularcompound be present through contamination and/or use in a minimal amountof a composition, mixture, or ingredients, the amount of the compoundshall be less than about 3 wt-%. More preferably, the amount of thecompound is less than 2 wt-%, less than 1 wt-%, and most preferably theamount of the compound is less than 0.5 wt-%.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.), or fabricsurfaces, e.g., knit, woven, and non-woven surfaces (such as surgicalgarments, draperies, bed linens, bandages, etc.), or patient-careequipment (such as respirators, diagnostic equipment, shunts, bodyscopes, wheel chairs, beds, etc.), or surgical and diagnostic equipment.Health care surfaces include articles and surfaces employed in animalhealth care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with acomposition according to the present invention. As used herein, thephrases “medical instrument,” “dental instrument,” “medical device,”“dental device,” “medical equipment,” or “dental equipment” refer toinstruments, devices, tools, appliances, apparatus, and equipment usedin medicine or dentistry. Such instruments, devices, and equipment canbe cold sterilized, soaked or washed and then heat sterilized, orotherwise benefit from cleaning in a composition of the presentinvention. These various instruments, devices and equipment include, butare not limited to: diagnostic instruments, trays, pans, holders, racks,forceps, scissors, shears, saws (e.g. bone saws and their blades),hemostats, knives, chisels, rongeurs, files, nippers, drills, drillbits, rasps, burrs, spreaders, breakers, elevators, clamps, needleholders, carriers, clips, hooks, gouges, curettes, retractors,straightener, punches, extractors, scoops, keratomes, spatulas,expressors, trocars, dilators, cages, glassware, tubing, catheters,cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, andarthoscopes) and related equipment, and the like, or combinationsthereof.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, andsome algae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the terms “mixed” or “mixture” when used relating to“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one peroxycarboxylic acid,such as a composition or mixture including peroxyacetic acid (POAA) andperoxyoctanoic acid (POOA).

As used herein, the terms “mixed,” “mixture” or “more than one” whenused relating to esters suitable for use in forming the compositions ofthe invention refer to a composition or mixture including more than oneester group undergoing a perhydrolysis reaction to form theperoxycarboxylic composition. The use of at least one ester of apolyhydric alcohol and a C1 to C18 carboxylic acid according to theinvention includes the use of various forms of the ester, such as themono, di, tri and/or mixtures thereof formations of the particularester. Accordingly, examples of suitable forms of esters for use as“mixtures” or comprising “more than one” include, but are not limitedto, glycerol monooctanoate, glycerol dioctanoate, glycerol trioctanoate,sorbitan monooctanoate, sorbitan dioctanoate, sorbitan trioctanoate, andmixtures and derivatives thereof. Further, as one skilled in the artshall ascertain based upon the description of the invention disclosedherein, the use of an ester source, such as glycerol octanoate, mayfurther comprise the use of the mono, di and tri esters and/or mixturesthereof. According to various embodiments of the invention, the use of“an” ester, such as octanoic glyceride, may include the use of a“mixture” of esters wherein more than one formation of the ester ispresent, including for example the mono, di and tri formations and/ormixtures thereof.

As used herein, the phrases “objectionable odor,” “offensive odor,” or“malodor,” refer to a sharp, pungent, or acrid odor or atmosphericenvironment from which a typical person withdraws if they are able to.Hedonic tone provides a measure of the degree to which an odor ispleasant or unpleasant. An “objectionable odor,” “offensive odor,” or“malodor” has an hedonic tone rating it as unpleasant as or moreunpleasant than a solution of 5 wt-% acetic acid, propionic acid,butyric acid, or mixtures thereof.

As used herein, the terms “peracid” or “peroxy acid” refer to an acidhaving the hydrogen of the hydroxyl group replaced by a hydroxy group.Oxidizing peracids are referred to herein as peroxycarboxylic acids.

As used herein, the term “polyhydric alcohol” or “polyol,” refers to analcohol that has two or more hydroxyl groups. Polyhydric alcoholssuitable for use in the compositions include, but are not limited to,sugars, sugar alcohols, and mixtures and derivatives thereof.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25+/−2° C., against several test organisms.

As used herein the term “sugar” refers to carbohydrates including one,two, or more saccharose groups. Sugars are a group of organic compoundsrelated by molecular structure that comprise simpler members of thegeneral class of carbohydrates. Each sugar consists of a chain of 2 to 7carbon atoms (usually 5 or 6). Sugars have the general formulaC_(n)H_(2n)O_(n), wherein n is between 2 and 7. One of the carbonscarries aldehydic or ketonic oxygen which may be combined in acetal orketal forms and the remaining carbon atoms usually bear hydrogen atomsand hydroxyl groups. In general, sugars are more or less sweet, watersoluble, colorless, odorless, optically active substances which losewater, caramelize and char when heated. Exemplary sugars include, butare not limited to, glucose, sucrose, lactose and mixtures thereof.

As used herein, the term “sugar alcohol” refers to the hydrogenated formof a carbohydrate, wherein the carbonyl group of the carbohydrate hasbeen reduced to a primary or secondary hydroxyl group. Sugar alcoholshave the general formula CH₂OH(CHOH)_(n)CH₂OH, wherein n is from 2 to 5.Exemplary sugar alcohols include, but are not limited to, glycol,ethylene glycol, propylene glycol, glycerol, erythritol,pentaerythritol, threitol, arabitol, xylitol, ribitol, mannitol,sorbitol, sorbitan, dulcitol, iditol, inositol, isomalt, maltitol,lactitol, polyglycitol, 1,4-cyclohexane diol, and mixtures andderivatives thereof. In some embodiments, the sugar alcohol is selectedfrom ethylene glycol, propylene glycol, glycerol, polyglycerol,sorbitol, sorbitan, and mixtures and derivatives thereof.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition.

As used herein, the term “ware” refers to items such as eating andcooking utensils, dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “ware washing” refers towashing, cleaning, or rinsing ware. Ware also refers to items made ofplastic. Types of plastics that can be cleaned with the compositionsaccording to the invention include but are not limited to, those thatinclude polycarbonate polymers (PC), acrylonitrile-butadiene-styrenepolymers (ABS), and polysulfone polymers (PS). Another exemplary plasticthat can be cleaned using the compounds and compositions of theinvention include polyethylene terephthalate (PET).

As used herein, the term “waters” includes food process or transportwaters. Food process or transport waters include produce transportwaters (e.g., as found in flumes, pipe transports, cutters, slicers,blanchers, retort systems, washers, and the like), belt sprays for foodtransport lines, boot and hand-wash dip-pans, third-sink rinse waters,and the like. Waters also include domestic and recreational waters suchas pools, spas, recreational flumes and water slides, fountains, and thelike.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

Embodiments of the Invention

Related Applications herein, the production of peracids ex-situ using anonsite mixing system is a complex process. In particular, relatedapplications U.S. patent application Ser. No. 13/330,915 and U.S. Pat.No. 8,858,895, incorporated herein by reference in its entirety,disclose various embodiments of both batch and continuous generators foron-site generation of peracid chemistry. These applications demonstratethe variety of factors impacting the rate at which an ester precursor isconverted to a resultant peracid. This application provides methods forovercoming a significant limitation of using any adjustable biocideformulator or generator system disclosed therein—namely, temperatureadjustments for the efficient and cost-effective use of any adjustablebiocide formulator or generator system.

Temperature is a critical factor on the kinetics of both peracidproduction as well as the kinetics of peracid decomposition inside anyadjustable biocide formulator or generator system. In particular,temperature becomes important when considering the variable environmentsin which an ex-situ peracid adjustable biocide formulator or generatorsystem may be used. Often environments suitable for employing anadjustable biocide formulator or generator system might range intemperature from the very cold (e.g. about 34° F. (1° C.)) to the veryhot (e.g. about 122° F. (50° C.)). Exemplary on-site locations forgeneration of the peracid chemistry according to the invention mayinclude, for example, a cold or refrigerated dairy room. Alternatively,a warm ambient temperature would be expected from a process floor of amanufacturing plant where myriad of heat-generating machines arelocated. As a result, when an adjustable biocide formulator or generatorsystem and the particular raw starting materials (e.g. reagents) areused under these variable conditions they produce unique peracidproduction and degradation curves which impact the ability toconsistently deliver a required dose of chemistry. Establishing methodsfor eliminating these varying production and/or degradation curvesovercomes a significant limitation and results in the consistentgeneration of peracid chemistries regardless of ambient temperatureconditions.

According to an embodiment of the invention, the methods of theinvention solve the problem caused by having variable reactiontemperatures, which can negatively impact the output and stability of anex-situ peracid reaction. According to the invention, the ABF systemsand methods of use are insensitive to environmental (e.g. ambient)temperatures of the location of the apparatus and/or reagents used forthe generation of peracid chemistry.

In particular, in one aspect the invention temperature controls areprovided for the reaction vessel and/or reaction manifold to overcome(i.e. control) any variability in both environmental factors and heatgenerated during the progression of the reaction. In another aspect ofthe invention, temperature controls are provided to at least one rawstarting material (e.g. reagent) that is input into an adjustablebiocide formulator or generator system. According to additionalembodiments a combination of temperature controls may be provided.

Temperature Controls of Reaction Vessels and/or Manifolds

The methods according to the invention may comprise, consist of and/orconsist essentially of at least one temperature control for controllingthe temperature of a portion of the adjustable biocide formulator orgenerator system. In one aspect of the invention the temperaturecontrols comprise, consist of and/or consist essentially of adjusting orcontrolling the temperature of the reaction vessel and/or reactionmanifold. In another aspect of the invention the temperature controlscomprise, consist of and/or consist essentially of adjusting orcontrolling the temperature of at least one zone of the ABF system.Adjusting or controlling the temperature of a particular zone of the ABFsystem, such as the reaction vessel and/or reaction manifold, eliminatesvariability in temperature caused as a result of environmental factors.

According to an embodiment the temperature of raw starting materialsadded to an adjustable biocide formulator or generator system may varyas a result of ambient temperatures. In addition, according to anembodiment the temperature of the adjustable biocide formulator orgenerator system itself may vary as a result of ambient temperatures. Asa result, temperature controls of at least one zone of the system canadjust for changes in ambient temperature and/or adjust the temperaturefor the peracid reaction to overcome such ambient temperatures.Preferably, the temperature zone adjusts the temperature of the reactionvessel (or the reaction manifold for a continuous system).

In addition, adjusting or controlling the temperature of the reactionvessel and/or reaction manifold eliminates variability in temperaturecaused by heat generated during the progression of the reaction (e.g.exothermic reaction of forming peracid chemistry). As one skilled in theart will ascertain based on the disclosure of the present invention, thetemperature variation can vary significantly based on reactionconditions largely driven by heat of solution caused by dilution of thesource of alkalinity (e.g. NaOH (50%)), reaction of that source ofalkalinity with hydrogen peroxide and/or neutralization of acidity inthe composition. The amount of heat generated through the exothermicreaction is dependent on a number of factors including for example,scale of the reaction and heat transfer properties of the reactionvessel. An exemplary range of temperature variations observed accordingto the embodiments swings we deal with are typically in the 10-50° F.range.

According to an embodiment the control of the reaction vessel and/orreaction manifold temperature may require refrigeration and/or heating.In particular, in one aspect of the temperature control, the temperatureis kept cool enough that the chemistry has a reasonable stability windowonce the peracid has been formed to be dispensed (e.g. maintains within+/−10% of its max for at least about 1-10 minutes). The coolingtemperature control may be required to decrease the temperature as aresult of the exothermic reactions that may degrade the peracidcompositions of the invention. In addition, there are various safetyconsiderations for a system to avoid increases in temperature, forexample system temperatures in excess of 100° C. In an additional aspectof the temperature control, the temperature is kept warm enough that thereaction can reach the +/−10% max concentration in a reasonable periodof time (e.g. 1-5 minutes or 3-10 minutes).

The means for achieving the temperature control according to theseembodiments of the invention may include in one aspect the use of aconstant temperature range of the apparatus. According to thisembodiment the particular zone of the system to be temperaturecontrolled (e.g. reaction vessel and/or reaction manifold) is put intothe constant temperature zone housing a heat source. According to anembodiment of the invention, a continuous or flow through reactorembodied in a reaction manifold is more amenable to temperature controlthrough the use of heat exchangers than the batch-mode ABF systems. Thisis a result of the temperatures within specific zones of the reactionmanifold more easily controlled to achieve complex chemistries that aremore difficult to achieve when using a batch-mode ABF system.

Suitable mechanisms for a temperature control mechanism for use in thesystems and methods of the invention include, for example, externalheating or cooling of a zone (e.g. reaction vessel) and/or the internalheating of the reagents from within the reaction vessel. The temperaturecontrol means for increasing the temperature may further include a warmwater bath and/or a heating chamber. In an additional aspect of theinvention, a temperature control means for increasing the temperature ofthe ABF system includes the flushing of the system with a hot watersource. For example, a water source having a temperature of at leastabout 37° C. (100° F.), preferably at least about 48° C. (120° F.) isflushed through the system periodically (e.g. between batches) toincrease the temperature of the system.

Additional exemplary mechanisms for increasing the temperature of theABF system include the use of heat jacketing of the reaction vessel or ajacketed manifold within the system, which may be achieved through theuse of a heated water jacket, for example. In addition, furtherexemplary mechanisms for increasing the temperature of the ABF systeminclude the use of electro-heating films, heating mantles, heatexchangers and the like. One skilled in the art will ascertainadditional means for affording increases in temperature of at least aportion of the adjustable biocide formulator or generator system.

In another aspect of the invention, means for achieving the temperaturecontrol wherein a decrease in temperature is required may include acooling system in or around the particular zone of the system to betemperature controlled (e.g. reaction vessel and/or reaction manifold).For example, it may be desirable to have reaction vessels and/orreaction manifold under refrigeration. Additional mechanisms that may besuitable for use to cool a reaction vessel, reaction manifold and/orother components of the system may include, for example, a quenchingmode, increased surface area, cooling jacket, venting systems, coldfinger, and the like.

Temperature Controls of Reagents

The methods according to the invention may comprise, consist of and/orconsist essentially of at least one means of tempering a reagent usedaccording to the invention. For example, in one aspect a temperedreagent (e.g. water) may be input into a system according to theinvention to control the temperature of the adjustable biocideformulator or generator system and/or the generated chemistry.

Suitable mechanisms for tempering a reagent include the preheating ofthe reagent. For example, a stock solution of a reagent may be housedwithin a water bath (e.g. warming/cooling) to modify the temperature ofthe reagent above or below the ambient temperature, as applicable.Thereafter, the temperature adjusted reagent is provided to the ABFsystem in a preheated manner suitable for use according to the methodsof the invention.

Additional exemplary mechanisms for the tempering of a reagent includethe use of electric blankets, hot or cold rooms, submersible heaters andthe like. One skilled in the art will ascertain additional methods foradjusting the temperature of a reagent according to the invention.

Preferably, a reagent is heated (or cooled to temperature adjust asapplicable) to approximately between about 21° C. to about 60° C.(70-140° F.), preferably between about 26° C. to about 54° C. (80-130°F.), and more preferably between about 32° C. to about48° C. (90-120°F.).

ABF Systems for Making On-Site Peracid Compositions

All embodiments of the ABF systems disclosed in related applicationsU.S. patent application Ser. No. 13/330,915 and U.S. Pat. No. 8,858,895,herein incorporated by reference in its entirety, are suitable systemsfor application of the temperature controlled modifications disclosedherein according to the invention. The various descriptions, includingclaims, specification and figures, outlining ABF system for the on-sitegeneration of peracid chemistries are incorporated by reference herein.

According to an aspect of the invention, as used herein, the terms ABF,ABF system/apparatus/generator and the like refer equally to the variousembodiments of the invention disclosing the batch and continuous ABFapparatus and/or system. The ABF system produces peroxycarboxylic acidforming compositions, referring to the generation of peroxycarboxylicacids in situ, in a non-equilibrium reaction. In particular embodimentsof the invention, the ABF generator system produces the anion capable offorming peroxycarboxylic acid upon acidification. According toadditional aspects of the invention, the ABF system may produceperoxycarboxylic acids.

Beneficially, the ABF systems according to the invention provide forapparatuses designed to produce peracid chemistry in either a continuousmanner or in batch preparations. These variations of the embodiments ofthe invention are capable of supplying chemistries in large and/or smallquantities and production rates. Regardless of the generation modeand/or mechanism the ABF systems according to the invention generateperacid chemistry that goes to completion within less than about 30minutes. In addition, without regard to the generation mode and/ormechanism the ABF systems according to the invention, theperoxycarboxylic acid forming composition and/or peracid compositionmaintains a peracid concentration within about 10% of its finalcompletion concentration for at least about 1 minute, at least about 2minutes, at least about 3 minutes, at least about 4 minutes, at leastabout 5 minutes, preferably within at least about 5-10 minutes, and morepreferably for more than at least 10 minutes.

According to an embodiment, the peracid concentration achieved isbetween about 0.25 wt-% to about 20 wt-%. Preferably, the peracidconcentration is at least about 4 wt-%, more preferably at least about 5wt-%, and still more preferably at least about 6wt-% or at least about 7wt-%. According to a preferred embodiment of the invention, the methodsand systems of the present invention achieve particular peracidconcentrations of peroxyacetic acid of at least about 6 wt-% andperoxyoctanoic acid of at least about 7 wt-%.

In some aspects, the system for on-site generation of peroxycarboxylicacid forming compositions may comprise, consist of and/or consistessentially of an apparatus for on-site peroxycarboxylic acid formingcomposition generation that is insensitive to environmental temperaturesof the location of the apparatus and/or reagents comprising a reactionvessel, a series of feed pumps, an outlet for dosing a peroxycarboxylicacid forming composition from said reaction vessel and a controller fora user- or system-inputted selection device. The apparatus of theinvention is further defined by the embodiments of feed pumps in fluidconnection with the reaction vessel and supply the reagents to producesaid peroxycarboxylic acid forming composition in the reaction vessel.Further embodiments include the reaction vessel in fluid connection withsaid outlet to dispense the peroxycarboxylic acid forming composition.According to the beneficial embodiments of the invention, thetemperature controlled mechanism maintains a controlled temperature ofthe reaction vessel and/or one or more reagents.

In additional preferred embodiments of the system, the mix order ofreagents are controlled to produce a consistent output of peracidchemistry without any fouling (e.g. precipitation or phase separation)of the reagents. In further aspects, the system employs an alkalinitysource that is sodium hydroxide (e.g. caustic soda). Further, the sodiumhydroxide is provided to the reaction vessel prior to the addition ofthe ester in a solution that is less than about 20 wt-% sodium hydroxideon an actives basis. In one aspect of the invention, the source ofalkalinity (e.g. sodium hydroxide or caustic soda) is combined withwater (e.g. diluted) prior to the addition of the ester source. Asdisclosed herein the ester source can further be provided in an esterpremix (e.g. ester/peroxide premix).

In additional preferred embodiment of the invention, the concentrationof the source of alkalinity are controlled to produce a consistentoutput of peracid chemistry without any fouling (e.g. precipitation) ofthe reagents. In particular a NaOH solution that is no more than 20 wt-%on an actives basis is obtained by diluting the NaOH with a water sourcebefore the ester component is combined with the reagents. Although notintending to be limited according to any theory of the invention and/ormechanism of action, the invention demonstrates superior peracidgeneration when a system delivers a source of alkalinity (e.g. NaOHsolution) source that is no more than 20% on an actives basis beforecombining with the ester reagent to initiate the peracid productionreaction.

According to preferred embodiments of making the peracid chemistry, anex-situ ABF generator system using an injection manifold to combine analkaline source, an ester precursor, a peroxygen source and optionallywater for production of a peroxy acid is used. Preferably the alkalinesource is caustic soda, wherein the caustic stream feeding the manifoldis less than about 20% by weight. In an aspect the caustic can bediluted within the manifold to the target concentration of less thanabout 20% by weight. In an additional embodiment, the ester is added tothe system downstream (e.g. after the addition of the diluted NaOHsolution).

The systems may further comprise, consist of and/or consist essentiallyof at least one measurement device, wherein said measurement devicemeasures one or more reaction kinetics or system operations for saidperoxycarboxylic acid forming composition generation selected from thegroup consisting of fluorescence, weight, flow, capacitive level, pH,oxidation reduction potential, pressure, temperature and combinationsthereof. Such measurement devices are those suitable to measure one ormore reaction kinetics or system operations for the generation ofperoxycarboxylic acid forming compositions, including for exampledevices to measure fluorescence, weight, flow (e.g. flow meters orswitches), capacitive level, pH, oxidation reduction potential,pressure, temperature and combinations thereof. Such measurement devicesmay measure the system's feed pumps, reaction vessels, reservoir,outlets, etc. Examples of additional suitable measurement devicesinclude capacitive level sensors, out of product alarms, POA/peroxidemonitors, oxychecks, IR/UV/VIS spectroscopy and pressure switches. Stillfurther examples of suitable measurement devices are disclosed herein,in addition various embodiments of those disclosed in U.S. patentapplication Ser. No. 12/108,202, and U.S. Pat. No. 7,547,421, bothentitled Apparatus and Method for Making Peroxycarboxylic Acid, whichare herein incorporated by reference in their entirety.

According to a further embodiment, the systems may comprise, consist ofand/or consist essentially of an additional feed pump providing an acidor acidic aqueous solution in fluid communication with the reactionmanifold or said reservoir. This feed pump is used to provide the acidor acidic aqueous solution to dilute the peroxycarboxylic acid formingcomposition to form a peroxycarboxylic acid having a pH of about 1.0 toabout 8.0. According to an embodiment the neutralization with the acidor aqueous acidic solution takes place when the concentration of peracidis within about 10% of its final concentration.

According to further embodiments, the systems may comprise, consist ofand/or consist essentially of an sources of additional reagents asdisclosed according to the compositions of the invention herein. Oneskilled in the art will ascertain the non-limiting examples of thesystems herein are further understood to include the various embodimentsof the invention disclosed with regard to the compositions and methodsof making the same according to the invention (e.g. use ofadditional/alternative reagents, reagent formulations, input means,order of mixing/adding reagents, and the like).

In some aspects of the invention, the system may include a variety ofsafety mechanisms. Exemplary on-site safety feedback mechanisms for asystem are disclosed in further detail in U.S. Patent Publication No.2009/0208365, which is hereby expressly incorporated by referenceincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof. Various safetymechanisms can measure pressure, temperature, difference in pressure,difference in temperature, or a combination thereof and provide aperceptible signal if one or more of these increases above apredetermined level. The level of pressure, temperature, difference inpressure, difference in temperature, or a combination thereof at whichsafety system provides a perceptible signal can be selected to allowintervention to avoid undesirable or unsafe conditions.

In some aspects, the system for making on-site peracid chemistryformulations further comprises an optional controller or softwareplatform. The software platform provides a user or system to select ageneration mode for a desired peracid formulation for on-sitegeneration. As a result, use of the system for onsite peracid chemistrygeneration provides significant user flexibility to generate chemistriesfor particular user-identified purposes. For example, the controller orcontrol software for operation of the system may permit a user or systemto select both the peracid formulation and the desired volume of theformulation for on-site generation. In a further aspect, the controlsoftware may determine the timing, sequencing and/or selection offeeding raw materials (e.g. reagents) into the system, mixing time andtotal reaction time required for production of the user- orsystem-selected peracid formulation.

According to the invention, the controller may further include amechanism for manually starting/stopping any of the same functions,including for example a manual switch panel for the same. In addition tomanual controls, such as a manual switch panel, the controllerpreferably has buttons or other means for selecting particularembodiments according to option displayed by the control softwareplatform. An embodiment of the controller may further include a displayscreen to assist a user in selecting a generation mode for a desiredperacid formulation and any other options for user selection as oneskilled in the art will ascertain based upon the description of theinvention. Concomitant with the control software are user-friendlyinstructions for use displayed on the display screen (or the like).

In an aspect of the invention, the control software utilizes a controlsoftware algorithm to maximize on-site active chemistry yield andprovide safe operating conditions for the reactor vessel(s) of thesystem. The control software permits user-identified chemistryproduction to be run in one or multiple reaction vessels and to properlysequence reactions to obtain active chemistries.

Examples of suitable controllers are disclosed herein, in additionvarious embodiments of those disclosed in U.S. patent application Ser.No. 12/108,202, and U.S. Pat. No. 7,547,421, both entitled Apparatus andMethod for Making Peroxycarboxylic Acid, which are herein incorporatedby reference in their entirety.

In another aspect of the invention, the system may include a data outputmeans for sharing information related to the peroxycarboxylic acidforming compositions and/or peroxycarboxylic acid formulations generatedaccording to the system. For example, an information backbone may beused to both collect and disseminate data from the process of generatingthe peracid formulations including, for example, compositionconsumption, dispensing or usage, and additional formulationproduction-related data. Such data may be generated in real-time and/orprovided in a historical log of operational data detectable or storableby a user or system. In an embodiment of the invention a user or systemis able to monitor usage and performance, including for example,chemistry dispensing, managing chemistry distribution to variouspoint-of-use applications, communication with system operators tocontrol and monitor chemistry dispensing, allocation and/or formulationand the like. According to an additional embodiment of the invention, auser or system is able to control systems, including program systems,remotely.

According to an aspect of the invention, any system operations suitablefor use with the invention may be controlled and/or monitored from aremote location. Remote system operations control and/or monitoring mayfurther include the system updates and/or upgrades. According to anaspect of the invention updates and/or upgrades to system operations maybe downloaded remotely. These and other embodiments of data outputmeans, information sharing, remote system operations and the like, whichmay be adapted for use with the present invention, are furtherdescribed, for example, in U.S. Pat. Nos. 7,292,917, 6,895,307,6,697,706 and 6,377,868 and U.S. Patent Publication Nos. 2005/0102059,2005/0065644, 2004/0088076, 2003/0195657 and 2003/0195656, which arehereby expressly incorporated by reference including, withoutlimitation, the specification, claims, and abstract, as well as anyfigures, tables, or drawings thereof.

In another aspect of the invention, the data output for sharinginformation related to the compositions according to the system maycoordinate multiple systems on at a single site. According to thisembodiment of the invention, information sharing between the multiplesystems may take places place using any communications network capableof coupling one or more systems according to the present invention,including for example, using a server computer and a database.

Exemplary Systems Depicted by Figures

According to an embodiment of the invention, as shown in FIG. 1, a useror process controller input, such as a CIP or tunnel washer processcontroller, selects a peracid formulation desired for on-site generationfor a specific cleaning application. The user or process controllerinput selects both the chemistry formulation and how much is needed(i.e., gallons use solution) and such input information is loaded intothe ABF system. Control software, including a software algorithm, may beused to calculate the timing and sequencing for dosing the raw materialsneeded for the particular peracid chemistry generation. Raw materialsare fed into the reaction vessels of the system under controlled mixtureand reaction times. The system may employ a variety of measurementdevices providing feedback to the system. Optionally, for generation ofa peroxycarboxylic acid formulation (as opposed to the anionperoxycarboxylic acid forming compositions), the stability of thereaction intermediates may be enhanced by adding an acid or aqueousacidic solution. The system provides the user or process controllerselected peracid formulation for use in a cleaning process, includingwithout limitation, antimicrobial, bleaching, sanitizing and/orantiscaling applications. In addition, various data output andinformation sharing methods may optionally be employed according to themethods and systems of the invention.

FIGS. 2A and 2B show diagrams of an embodiment of an adjustable biocideformulator apparatus according to the invention, including descriptionof the dosing of raw starting materials (e.g. reagents) for thegeneration of peracid chemistries according to the invention. Inparticular, FIG. 2A shows a process flow of methods of making theperacid chemistry using the apparatus according to the invention. Themethods set forth can be utilized using either a batch or a continuousgenerator according to the various embodiments of the invention. As setforth, methods of the invention include the steps of peracid generation,a period of reaction holding time followed by evacuation of the line,dilution with water of the concentrated chemistry and optionallyacidification.

FIG. 2B further shows a non-limiting example of a method of peracidchemistry according to FIG. 2A. In the non-limiting example peracidgeneration includes the injection of raw starting materials (e.g.reagents). In particular, the injection of NaOH 12 and water 14 arecombined in injection manifold 21. The injection manifold is not limitedaccording to a particular structure or apparatus. According to apreferred embodiment, the caustic is diluted to a concentration of lessthan or equal to about 20% by weight. The NaOH 12 and water 14 arepreferably homogenized or mixed by passing through a mixer 35.Thereafter, the an ester premix or ester and peroxide 16 are injectedinto another injection manifold 21 of the system. According to thisaspect of the invention the ester premix or ester and peroxide are addedto the dilute NaOH for improved chemistry generation. The ester premixor its individual components 16 are homogenized or mixed 35 with thecaustic stream. Following the mixing, the reagents are held for thereaction to go to completion within a reaction manifold 22. Notably, theholding step can occur direction in a dilution tank 34 or optionally inan intermediate reaction manifold 22. Following the reaction hold timethe reaction manifold 22 is purged with water then air into a dilutionvessel 34 (e.g. line evacuation). Then water 14 is used for the dilutionstep within the dilution tank 34 to dilute the concentrated chemistry.In a further aspect the diluted chemistry can be acidified using an acidor aqueous acid solution 18 within the dilution vessel 34 (or optionallywithin the reaction manifold 22—not depicted in the figure). Uponcompletion of the peracid generation as depicted in FIGS. 2A-B a watersource 14 may be used to flush the system at a high flow rate.

Apparatus Dosing

The apparatus of the ABF system overcomes the raw material feed designchallenge of accurately dosing raw materials. According to theinvention, liquid based raw materials must be dosed into reactionvessel(s) quickly. For example, according to an embodiment of theinvention, the sugar ester is the limiting reaction ingredient andrequires accurate dispensing of the raw material. An example of asuitable sugar ester is sorbital octanoate and/or glyceryl octanoate,which are viscous liquids that are difficult to accurately measure. As aresult, pump selection is critical and accommodating pumpcharacteristics with software is a critical embodiment of the ABFsystem.

The dispensing precision required to prepare small batch sizes is morecritical than larger batches, as a result of the dispensing errorbecoming a larger percentage of the dispensed peracid chemistries. As aresult, the apparatus of the ABF system provides feed pumps to reducethe presence of air bubbles in the delivery line altering the amount ofsugar ester chemistry dispensed and reducing the overall yield of thereaction. In addition to providing suitable feed pumps, theconcentration of the sugar ester may be diluted to increase dosingaccuracy. Such methods improve the dosing accuracy and decreasevariations in volumetric flow of reagents according to the invention. Inaddition to the reduction of air bubbles in a delivery line, thedispensing precision according to the invention delivers the reagents ata constant flow rate over long durations of time, thereby reducingand/or eliminating the need for recalibration of the apparatus.

According to an alternative embodiment of the invention, a viscositymodifier may be added to the sugar ester. A viscosity modifier is afurther example of a suitable raw material 28 according to theinvention. Viscosity modifiers according to the invention may be used toadjust the rheology of a reagent in order to reduce the viscosity tomake a raw material more suitable for use in the apparatus and systemaccording to the invention, namely rendering the raw materialsignificantly easier to pump.

Apparatus Rinsing

Rinsing of the ABF system has an impact on yield. According to anembodiment of the invention, adequate rinsing of the reactor vessel(s)and feed pump lines is necessary. According to a preferred embodiment ofthe invention, the control software of the ABF system may be used toestablish a process for system rinsing both reactor vessel(s) and feedpump lines. Remaining water after rinsing or flushing does not have anegative impact on the system. Water remaining in the mixing manifoldimparts a dilution factor for which the dilution factor can beaccommodated in the formulation. However, reaction intermediates must berinsed from the system, as any reacted chemistry not flushed impacts theyield of a subsequent batch. This is a result of residual reactionintermediates in the system imparting unknown actives concentration dueto the instability of the product at high pH over time. In addition,according to an embodiment an air-purge may be further employed afterrinsing of the apparatus according to the invention, which as oneskilled in the art will appreciate effectively removes nearly all liquidcontent from the manifold after a water rinse.

Preferably, the ABF system, including the reaction vessels, is cleanedbetween batches of peroxycarboxylic acid forming compositions. Accordingto an embodiment of the invention, the system is rinsed (e.g. feed pumplines flushed) with warm/hot water between batches, and/or at regularlyschedules intervals to comply with regulatory requirements (e.g.sanitizing regulations), as one skilled in the art shall ascertain.According to embodiments employing a continuous system the feed pumplines (including reaction manifold) may be rinsed at scheduledincrements.

Compositions

The embodiments of the invention are suitable for generating theperoxycarboxylic acid chemistries (as well as the anion peroxycarboxylicacid forming compositions) which are disclosed in further detail in therelated U.S. patent application Ser. Nos. 61/427,965, 13/331,304, nowissued U.S. Pat. No. 8,846,107, and Ser. No. 13/331,486, entitled InSitu Generation of Peroxycarboxylic Acids at Alkaline pH and Methods ofUse Thereof, which are herein incorporated by reference in its entirety.In addition to the chemistries generated, these applicationsincorporated by reference further disclose the particular raw startingmaterials (e.g. reagents) suitable for use in the ABF systems accordingto the invention to generate the particular chemistries.

In some embodiments, the system according to the present inventionproduces peroxycarboxylic acid forming compositions or peroxycarboxylicacid compositions for use in a variety of cleaning applications. Thecompositions have enhanced stability. According to an embodiment of theinvention, the peroxycarboxylic acid forming compositions are stable forup to 24 hours providing suitable stability for on-site generation andusage for a variety of cleaning applications. According to a furtherembodiment, the peroxycarboxylic acid compositions are stable for up toat about 7 to 10 days.

In some aspects, the present disclosure relates to peroxycarboxylic acidforming compositions. That is, the compositions are capable ofgenerating peroxycarboxylic acids in situ, in a non-equilibriumreaction. Surprisingly, it has been found that the optimum pH for thegeneration of peroxycarboxylic acid compositions is greater than about12, or pH greater than about 13. It has also been found that mixedperoxycarboxylic acid compositions, viz. compositions that form two ormore peroxycarboxylic acids, can be generated in situ in accordance withthe methods disclosed herein. Peroxycarboxylic (or percarboxylic) acidsgenerally have the formula R(CO₃H)n, where, for example, R is an alkyl,aryl alkyl, cycloalkyl, aromatic, or heterocyclic group, and n is one,two, or three, and named by prefixing the parent acid with peroxy. The Rgroup can be saturated or unsaturated as well as substituted orunsubstituted.

In an embodiment of the invention the peroxycarboxylic acid formingcompositions comprise individual reagents combined according to theinvention. These reagents are described herein individually along andinclude at least one ester of a polyhydric alcohol and a C1 to C18carboxylic acid, an oxidizing agent, a source of alkalinity, solvents,and other functional groups. An acidulant is also described herein as areagent to be added to the compositions after the formation of thepercarboxylic acid(s). Alternatively, as described herein, there may bebenefits to providing the reagents in various premix formulations todecrease the number of reagents and/or increase the simplicity of theinvention. Each of these embodiments are described in further detailherein.

Esters

In some aspects, the compositions include an ester of a polyhydricalcohol and a C1 to C18 carboxylic acid. According to an embodiment, thepolyhydric alcohol may also include a sugar alcohol. The compositionscan also include more than one or a mixture of esters of a polyhydricalcohol and a C1 to C18 carboxylic acid. For example, in someembodiments, the compositions include two, three or four esters. Whenmore than one ester is present, the esters can be different. Forexample, in some embodiments, the compositions can include a first esterof a polyhydric alcohol and a C1 to C4 carboxylic acid, and a secondester of a polyhydric alcohol and a C5 to C11 carboxylic acid. Forfurther example, in some embodiments, the compositions can include afirst ester of a polyhydric alcohol and a C1 to C18 carboxylic acid in amono, di or tri-formation, and a second ester of a polyhydric alcoholand a C1 to C18 carboxylic acid in a mono, di or tri-formation. Oneskilled in the art will appreciate the various combinations of estersthat can be used for the compositions according to the invention.

An example of a suitable ester for use according to the invention isglycerol octanoate. Glycerol octanoate has multiple ester components andothers, including glycerol monooctanoate, glycerol dioctanoate, glyceroltrioctanoate and others (glycerin, fatty acid, water). An estimatedcomponent percentage of each is approximated at about 39.6% glycerolmonooctanoate, 24.5% glycerol dioctanoate, 1.42% glycerol trioctanoateand 34.5% of the others (glycerin, fatty acid, water).

The use of various forms of an ester (e.g. mono, di and/ortri-formations) to comprise a mixture of esters will impact the peracidyield of a particular composition according to the invention. Forexample, the various forms of the ester will have different kinetics ingenerating the peracids according to the methods of the invention. Forexample, in one aspect, a monooctanoate glycerol ester is faster ingenerating peracid than the di- or trioctanoate glycerol esters. Inaddition, the selection of the various forms of an ester will be furtherimpacted by the water solubility of the compositions and whether anyadditional ingredients are combined to affect solubility (e.g. solvents)that would favor the use of less soluble ester forms (e.g.tri-formations). Accordingly, one skilled in the art of reactionkinetics will ascertain the benefits of using various combinations ormixtures of esters according to the compositions and methods of theinvention.

The esters for use in the present invention include esters of polyhydricalcohols with carboxylic acid based leaving groups. A variety ofcarboxylic acids can be included. Carboxylic acids generally have theformula R(COOH)n, where, for example, R is an alkyl, aryl alkyl,cycloalkyl, aromatic, or heterocyclic group, and n is one, two, orthree. In some embodiments, the carboxylic acid leaving group is a C₅ toC₁₁ carboxylic acid. In some embodiments, the carboxylic acid leavinggroup is a C₁ to C₄ carboxylic acid. In other embodiments, thecompositions include two esters of polyhydric alcohols, each esterhaving a different carboxylic acid leaving group. For example, thecompositions can include a polyhydric alcohol ester with a C1 to C4carboxylic acid leaving group, and also include a polyhydric alcoholester with a C5 to C11 carboxylic acid leaving group.

Examples of suitable carboxylic acids include, but are not limited to,formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic,octanoic, nonanoic, decanoic, undecanoic, dodecanoic, as well as theirbranched isomers, lactic, maleic, ascorbic, citric, hydroxyacetic,neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic,glutaric, adipic, pimelic subric acid, and mixtures thereof.

Without wishing to be bound by any particular theory, it is thought thatthe esters included in the compositions undergo a perhydrolysisreaction, thereby forming the peroxycarboxylic composition. An exemplaryperhydrolysis reaction in accordance with the present disclosure isillustrated below:

As can be seen from this illustration, it is thought the oxidizingagent, H₂O₂, perhydrolyzes the ester bond, thereby forming thepercarboxylic acid corresponding to the cleaved carboxylic acid group.In contrast to an acid catalyzed equilibrium reaction, the reaction isstoichiometric, i.e. no excess amounts of the reactants are required forthe reaction. The kinetics of the reaction are pH dependent, and thereaction can reach the maximum yield in the order of minutes. Esterssuitable for use include, but are not limited to, monooctanoicglyceride, dioctanoic glyceride, trioctaonoic glyceride, polyglyceroloctanoate, sorbitan monooctanoate, sorbitan dioctanoate, sorbitantrioctanoate, laurate sucroside and mixtures and derivatives thereof.

The compositions include the esters in an amount sufficient to generatethe desired amount of percarboxylic acid. In some embodiments, thecompositions include about 0.01 wt-% to about 95 wt-% of the ester,about 0.1 wt-% to about 50 wt-% of the ester, or about 1 wt-% to about10 wt-% of the ester. In some embodiments, more than one ester ispresent in the compositions. Each ester can be present in thecompositions at the above stated weight percents.

Unlike conventional acid catalyzed equilibrium peroxycarboxylic acidforming compositions, the compositions of the present invention can beformed using a non-equilibrium perhydrolysis reaction. Thus, an excessamount of the starting reagents is not needed. Accordingly, afterformation of the peroxycarboxylic acid, the compositions contain lesscarboxylic acid and more peroxycarboxylic acid than an equivalentequilibrium reaction. In some embodiments, the compositions containabout 1 part percarboxylic acid for every about 1 part carboxylic acidafter perhydrolysis, or about 6 part percarboxylic acid for every about1 part carboxylic acid after perhydrolysis. In some embodiments, thecompositions are free of or substantially free of carboxylic acids afterthe perhydrolysis reaction.

Alkalinity Source

The compositions also include a source of alkalinity. The source ofalkalinity can include, but is not limited to, an alkaline metalhydroxide, an alkaline earth metal hydroxide, an alkali metal silicate,an alkali metal carbonate, borates and mixtures thereof. Suitablealkaline metal hydroxides include, but are not limited to, sodiumhydroxide, potassium hydroxide and mixtures thereof. Suitable alkalineearth metal hydroxides include, but are not limited to, magnesiumhydroxide, calcium hydroxide and mixtures and derivatives thereof.Suitable alkali metal silicates include but are not limited to, sodiumsilicate and derivatives thereof. In other embodiments, an alkali metalcarbonate can be used as a source of alkalinity. For example, in someembodiments, sodium carbonate, sodium bicarbonate or mixtures andderivatives thereof can be used.

The source of alkalinity can be present in the compositions in an amountsufficient to provide the desired pH. In some embodiments, thecompositions have a pH greater than about 12, greater than about 12.5,or greater than about 13. In some embodiments, the alkaline source ispresent in the composition from about 0.001 wt-% to about 50 wt-%, fromabout 1 wt-% to about 30 wt-%, or about 10 wt-% to about 25 wt-%. Insome embodiments, the alkaline source is present at from about 25 wt-%to about 50 wt-% of the composition. It is to be understood that allranges and values between these ranges and values are encompassed by thepresent disclosure.

Oxidizing Agent

The compositions also include an oxidizing agent. The oxidizing agentmay include a peroxide source. Oxidizing agents suitable for use withthe compositions include the following types of compounds or sources ofthese compounds, or alkali metal salts including these types ofcompounds, or forming an adduct therewith: hydrogen peroxide,urea-hydrogen peroxide complexes or hydrogen peroxide donors of: group 1(IA) oxidizing agents, for example lithium peroxide, sodium peroxide;group 2 (IIA) oxidizing agents, for example magnesium peroxide, calciumperoxide, strontium peroxide, barium peroxide; group 12 (IIB) oxidizingagents, for example zinc peroxide; group 13 (IIIA) oxidizing agents, forexample boron compounds, such as perborates, for example sodiumperborate hexahydrate of the formula Na₂[B₂(O₂)₂(OH)₄].6H₂O (also calledsodium perborate tetrahydrate); sodium peroxyborate tetrahydrate of theformula Na₂B₂(O₂)₂[(OH)₄].4H₂O (also called sodium perboratetrihydrate); sodium peroxyborate of the formula Na₂[B₂(O₂)₂(OH)₄] (alsocalled sodium perborate monohydrate); group 14 (IVA) oxidizing agents,for example persilicates and peroxycarbonates, which are also calledpercarbonates, such as persilicates or peroxycarbonates of alkalimetals; group 15 (VA) oxidizing agents, for example peroxynitrous acidand its salts; peroxyphosphoric acids and their salts, for example,perphosphates; group 16 (VIA) oxidizing agents, for exampleperoxysulfuric acids and their salts, such as peroxymonosulfuric andperoxydisulfuric acids, and their salts, such as persulfates, forexample, sodium persulfate; and group VIIa oxidizing agents such assodium periodate, potassium perchlorate. Other active inorganic oxygencompounds can include transition metal peroxides; and other suchperoxygen compounds, and mixtures thereof.

In some embodiments, the compositions of the present invention employone or more of the inorganic oxidizing agents listed above. Suitableinorganic oxidizing agents include ozone, hydrogen peroxide, hydrogenperoxide adduct, group IIIA oxidizing agent, or hydrogen peroxide donorsof group VIA oxidizing agent, group VA oxidizing agent, group VIIAoxidizing agent, or mixtures thereof. Suitable examples of suchinorganic oxidizing agents include percarbonate, perborate, persulfate,perphosphate, persilicate, or mixtures thereof.

In some embodiments, the oxidizing agent includes hydrogen peroxide, ora source or donor of hydrogen peroxide. In other embodiments, theoxidizing agent includes a peroxide source selected from a percarbonate,a perborate urea hydrogen peroxide, PVP-peroxides and mixtures thereof.

The compositions may contain an effective amount of an oxidizing agent.In some embodiments, the compositions include about 0.001 wt-% to about60 wt-% of the oxidizing agent, or about 1 wt-% to about 25 wt-% of theoxidizing agent. In some embodiments, the compositions include about 30wt-% to about 50 wt-% of the oxidizing agent. It is to be understoodthat all ranges and values between these ranges and values areencompassed by the present invention.

Solvent

In some embodiments, the compositions of the invention further include asolvent. In some embodiments, the solvent is water. The water may beprovided by the use of aqueous reagents, viz. oxidizing agent,alkalinity source. In other embodiments, an additional amount of wateris added to the compositions. The compositions may be free of orsubstantially free of any added water. A non-aqueous solvent may also beused in the compositions. For example, in some embodiments, an alcoholis included as a solvent in the compositions.

The compositions may include an effective amount of solvent. In someembodiments, the compositions may include about 10 wt-% to about 99 wt-%of a solvent, or about 20 wt % to about 80 wt-% of a solvent. In otherembodiments, the compositions may include more than about 30 wt-%, morethan about 50 wt-%, more than about 60 wt-% or more than 70% of asolvent. It is to be understood that all values and ranges between thesevalues and ranges are encompassed by the present invention.

Eliminated Functional Ingredients

Unlike conventional equilibrium based peroxycarboxylic acidcompositions, the compositions disclosed herein are formed from anon-equilibrium reaction. Further, the composition disclosed herein canbe used immediately after generation. Thus, many of the additionalingredients required in equilibrium based compositions do not need to beincluded in the present compositions. In some embodiments stabilizingagents are preferred for certain compositions according to the inventionand provide benefits. However, beneficially, the use of non-equilibriumchemistry according to the present invention optionally provides thatthe compositions can be free of, or substantially free of a stabilizingagent.

Stabilizing agents are commonly added to equilibrium peroxycarboxylicacid compositions to stabilize the peracid and hydrogen peroxide andprevent the decomposition of these constituents within the compositions.Various embodiments of the invention do not require the use of at leastone or more of such stabilizing agents. Examples of stabilizing agentsmay include for example, surfactants, couplers, hydrotropes, acidcatalysts and the like that are conventionally used in equilibriumperacid compositions to stabilize and improve shelf life of thecomposition.

Further examples of stabilizing agents include, for example, chelatingagents or sequestrants. Such sequestrants include, but are not limitedto, organic chelating compounds that sequester metal ions in solution,particularly transition metal ions. Such sequestrants include organicamino- or hydroxy-polyphosphonic acid complexing agents (either in acidor soluble salt forms), carboxylic acids (e.g., polymericpolycarboxylate), hydroxycarboxylic acids, aminocarboxylic acids, orheterocyclic carboxylic acids, e.g., pyridine-2,6-dicarboxylic acid(dipicolinic acid). Dipicolinic acid, 1-hydroxyethylidene-1,1-diphosphonic acid (CH3C(PO3H2)2OH) (HEDP) are furtherexample of stabilizing agents.

Additional examples of stabilizing agents commonly used in equilibriumchemistry to stabilize the peracid and hydrogen peroxide and/or preventthe premature oxidation of the composition include phosphonic acid orphosphonate salt. Phosphonic acids and phosphonate salts include HEDP;ethylenediamine tetrakis methylenephosphonic acid (EDTMP);diethylenetriamine pentakis methylenephosphonic acid (DTPMP);cyclohexane-1,2-tetramethylene phosphonic acid; amino[tri(methylenephosphonic acid)]; (ethylene diamine[tetra methylene-phosphonic acid)];2-phosphene butane-1,2,4-tricarboxylic acid; or salts thereof, such asthe alkali metal salts, ammonium salts, or alkyloyl amine salts, such asmono, di, or tetra-ethanolamine salts; picolinic, dipicolinic acid ormixtures thereof. In some embodiments, organic phosphonates, e.g., HEDPare well known as used stabilizing agents.

Exemplary commercially available food additive chelating agents includephosphonates sold under the trade name DEQUEST® including, for example,1-hydroxyethylidene-1,1-diphosphonic acid, available from MonsantoIndustrial Chemicals Co., St. Louis, Mo., as DEQUEST® 2010;amino(tri(methylenephosphonic acid)), (N[CH₂PO₃H₂]₃), available fromMonsanto as DEQUEST® 2000; ethylenediamine[tetra(methylenephosphonicacid)] available from Monsanto as DEQUEST® 2041; and2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay ChemicalCorporation, Inorganic Chemicals Division, Pittsburgh, Pa., as BayhibitAM. Further exemplary sequestrant can be or include aminocarboxylic acidtype sequestrant. Suitable aminocarboxylic acid type sequestrantsinclude the acids or alkali metal salts thereof, e.g., amino acetatesand salts thereof. Suitable aminocarboxylates includeN-hydroxyethylaminodiacetic acid; hydroxyethylenediaminetetraaceticacid, nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid(EDTA); N-hydroxyethylethylenediaminetriacetic acid (HEDTA);diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diaceticacid; and the like; and mixtures thereof. Still further sequestrantsinclude polycarboxylates, including, for example, polyacrylic acid,maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid,acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide,hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamidecopolymers, hydrolyzed polyacrylonitrile, hydrolyzedpolymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrilecopolymers, polymaleic acid, polyfumaric acid, copolymers of acrylic anditaconic acid, phosphino polycarboxylate, acid or salt forms thereof,mixtures thereof, and the like.

Further, unlike conventional equilibrium based peroxycarboxylic acidcompositions, the present compositions can also be free of, orsubstantially free of surfactants. This is especially advantageous forcompositions incorporating C5 to C18 peroxycarboxylic acids. That is,under perhydrolysis conditions, the C5-C18 peroxycarboxylic acid anionsgenerated are water soluble. If the anions (e.g. peroxycarboxylicacid-forming compositions) are acidified for end use applications, theconcentrations of peroxycarboxylic acids are below the water solubilitylimit of the peroxycarboxylic acids. Thus, couplers are not needed tocouple the peroxycarboxylic acids in solution.

Additional Functional Ingredients

The compositions may also include additional functional ingredients.Additional functional ingredients suitable for use in the presentcompositions include, but are not limited to, acidulants, hydrotropes,dispersants, antimicrobial agents, optical tracers, solidificationagent, aesthetic enhancing agent (i.e., colorant (e.g., pigment),odorant, or perfume), among any number of constituents which can beadded to the composition. For example, suitable functional ingredientsfor various embodiments of the invention are hydrotropes, which may bedesired for producing clear compositions or dispersants which are moreefficient in producing homogeneous dispersions. Such adjuvants can bepreformulated with the present compositions or added to the compositionsafter formation, but prior to use. The compositions can also contain anynumber of other constituents as necessitated by the application, whichare known and which can facilitate the activity of the presentcompositions.

Acidulant

In an embodiment, the present compositions can include an acidulant. Theacidulant can be added to the compositions after the formation of thepercarboxylic acid. That is, an acidulant can be added to theperoxycarboxylic acid concentrate to form an acidified use solution. Theacidulant can be effective to form a use composition with pH of about 1or less. The acidulant can be effective to form a use composition withpH of about 8, about 8 or less, about 7, about 7 or less, about 6, about6 or less, about 5, about 5 or less, or the like. In some embodiments,the acidulant is present at an amount effective to form a use solutionwith a pH of about 6 to about 8, about 1 to about 8, or about 1 to about5. In a further embodiment, the acidulant may be added to a semi-dilutedreaction solution to produce meta-stable peracid composition.

Any suitable acid can be included in the compositions as an acidulant.In an embodiment the acidulant is an acid or an aqueous acidic solution.In an embodiment, the acidulant includes an inorganic acid. In someembodiments, the acidulant is a strong mineral acid. Suitable inorganicacids include, but are not limited to, sulfuric acid, sodium bisulfate,phosphoric acid, nitric acid, hydrochloric acid. In some embodiments,the acidulant includes an organic acid. Suitable organic acids include,but are not limited to, methane sulfonic acid, ethane sulfonic acid,propane sulfonic acid, butane sulfonic acid, xylene sulfonic acid,cumene sulfonic acid, benzene sulfonic acid, formic acid, acetic acid,mono, di, or tri-halocarboyxlic acids, picolinic acid, dipicolinic acid,and mixtures thereof. In some embodiments, the compositions of thepresent invention are free or substantially free of a phosphorous basedacid.

In an embodiment, the acidulant includes a carboxylic acid with pK_(a)less than 5. Suitable carboxylic acids with pK_(a) less than 5 includeacetic acid, hydroxyacetic acid, hydroxypropionic acid, otherhydroxycarboxylic acids, mixtures thereof, or the like. Such anacidulant is present at a concentration where it does not act as asolubilizer. In some embodiments, the compositions are free of, orsubstantially free of a carboxylic acid.

In certain embodiments, the present composition includes about 0.001 toabout 50 wt-% acidulant, about 0.001 to about 30 wt-% acidulant, about 1to about 50 wt-% acidulant, about 1 to about 30 wt-% acidulant, about 2to about 40 wt-% acidulant, about 2 to about 10 wt-% acidulant, about 3to about 40 wt-% acidulant, about 5 to about 40 wt-% acidulant, about 5to about 25 wt-% acidulant, about 10 to about 40 wt-% acidulant, about10 to about 30 wt-% acidulant, about 15 to about 35 wt-% acidulant,about 15 to about 30 wt-% acidulant, or about 40 to about 60 wt-%acidulant. The composition can include any of these ranges or amountsnot modified by about.

Premix Formulations

In an embodiment, the reagents described herein (e.g. at least one esterof a polyhydric alcohol and a carboxylic acid, source of alkalinity,oxidizing agent) may be combined into various premix formulations toreduce the number of raw starting materials required for the methods andcompositions and further simplify the methods of the invention.According to such an embodiment the providing of premix formulationsensures consistent and stable delivery of reagents.

Premix formulations suitable for use according to the invention maycomprise, consist of and/or consist essentially of at least one ester,an oxidizing agent and mixtures thereof. Premix formulations suitablefor use according to the invention may comprise, consist of and/orconsist essentially of at least one ester, an oxidizing agent, a solventand mixtures thereof. Premix formulations suitable for use according tothe invention may also comprise, consist of and/or consist essentiallyof at least one ester, an oxidizing agent, water, solvents, dispersingagents, and mixtures thereof.

As one skilled in the art will ascertain the use of premixes employsadditional function ingredients for purpose of stabilizing the premixconcentrate for use in the compositions and methods according to theinvention. For example, hydrotropes, dispersing agents and/or othersolvents may be desirable for maintaining the solubility and stabilityof a particular concentrated premix. The use of any couplers ordispersing agent (such as a surfactant) within a premix formulation isdistinct from the use of surfactants in the conventional generation andstorage of peracid chemistries, wherein couplers are critical toestablishing and maintaining a stable, clear solution of the generatedperacid chemistry.

According to the invention, the use of dispersing agents alone within aconcentrated premix formulation does not stabilize the premixcomposition. Rather the dispersing agents are provided in an amountsuitable for providing meta-stable peracid compositions generated fromthe premix after acidification, before further dilution for application.The most efficient dispersing agents were found to be anionicsurfactants, and this type of surfactant is known to have high foamingprofile. For applications which involves mechanical actions (e.g. CIPsanitizing), the high foam property of the composition is undesirable.Thus, in addition to economic reason, it is preferred to use a minimumamount of the dispersing agent to achieve a meta-stable peracidcomposition to meet the application of use requirements.

According to an embodiment of the invention less than about 10 ppm,preferably less than about 9 ppm, less than about 8 ppm, less than about7 ppm, less than about 6 ppm, less than about 5 ppm, less than about 4ppm, less than about 3 ppm, less than about 2 ppm, or less than about 1ppm of a dispersing agent is included in the generated peracid chemistryas a result of the use of a surfactant dispersing agent in aconcentrated premix formulation according to the invention. This isdistinct from the level of surfactants in use solutions of a traditionalperacid chemistry, where the amounts of surfactants are normally inexcess of about 50 ppm, in excess of about 60 ppm, in excess of about 70ppm, in excess of about 80 ppm, in excess of about 90 ppm, or in excessof about 100 ppm.

According to a further embodiment of the invention less than about 2%dispersing agent is present in the premix composition, wherein at leastabout 5%, about 6%, about 7%, about 8% or about 9% are required toprovide the stable, clear solution of a generated peracid chemistry whenacidified. This is distinct from the generated peracid chemistryaccording to the invention wherein a meta stable chemistry is generated.Although not wishing to be limited to a particular theory of mechanismof action of the invention, the generated meta-stable composition is amilky colored composition having stability for at least a few hours.

According to an embodiment of the invention, the use of a solvent (e.g.ethanol) is an efficient way to make a stable premix composition.Solvents suitable for the concentrated premix formulations according tothe invention include, for example, organic solvents such as alcohol,ether or ketone. Preferably, the solvent is a water soluble alcohol,such as ethanol, methanol, propanol, isopropanol and/or butanol. As oneskilled in the art will ascertain the various isomers of the solvents,including alcohols, are further included within the scope of thesolvents suitable for use with the concentrated premix formulations ofthe invention.

Beneficially, the use of concentrated premix formulation still does notrequire the use of any chelators and/or stabilizers. As a result,regardless of whether individual reagents or concentrated premixformulations are utilized according to the invention, both the reagentsand the peracid compositions generated according to the inventionprovide sustainable chemistries as a result of the elimination of theuse of various stabilizers and/or additional amounts of chemistryrequired to drive the formation of traditional peracid chemistry. As aresult of reduced input of reagents for the compositions according tothe invention (e.g. resulting from the use of a non-equilibriumreaction) there is a significantly reduced waste stream (e.g. anyreagents and/or percentage of composition not impacting themicro-efficacy of the compositions). Instead the present inventionprovides increased amounts of post-reaction products (e.g. peracids)with decreased amounts of unreacted reagents. In particular, accordingto the invention the systems generate higher concentrations of theperoxycarboxylic acid(s) and lower concentrations of hydrogen peroxide(e.g. unreacted reagents) than achieved in equilibrium systems.

In an aspect of the invention, a premix formulation may deliver theester of a polyhydric alcohol and a carboxylic acid and the oxidizingagent. In one aspect a premix formulation includes an ester of apolyhydric alcohol and a carboxylic acid, an oxidizing agent and adispersing agent. In another aspect a premix formulation includes anester of a polyhydric alcohol and a carboxylic acid, an oxidizing agent,a dispersing agent and water.

Suitable dispersing agents for use according to the concentrated premixformulations of the invention include polymers, surface active agents orany compounds which will help to achieve a meta-stable solution afterthe ester perhydrolysis through the interaction with the peroxy fattyacids generated through perhydrolysis. These may include, for example,sulfonated oleic acids (SOA), 1-octanesulfonic acid (NAS), sodium laurylsulfonates (SLS) and the like. In another aspect a premix formulationincludes an ester of a polyhydric alcohol and a carboxylic acid, anoxidizing agent and a solvent. Ethanol and methanol are examples ofsuitable solvents for use in stabilizing the concentrated premixformulation according to the invention. The use of the solvent incertain embodiments obviates the use of a dispersing agent for premixstability. However, in alternative embodiments a premix formulation mayinclude an ester of a polyhydric alcohol and a carboxylic acid, anoxidizing agent, a dispersing agent and a solvent. Without wishing to belimited to a particular theory or mechanism of action of the invention,the combined use of a dispersing agent and a solvent within aconcentrated premix formulation reduces the overall need for asurfactant dispersing agent in the premix composition.

In still another aspect a concentrated premix formulation includes anoxidizing agent and a dispersing agent.

In certain embodiments, the concentrated premix composition includesabout 0.001 to about 90 wt-% ester of the polyhydric alcohol and acarboxylic acid, about 0.1 to about 90 wt-% ester, about 1 to about 75wt-% ester, about 10 to about 75 wt-% ester, about 25 to about 75 wt-%ester, about 30 to about 70 wt-% ester, or about 30 to about 65 wt-%ester.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 99 wt-% oxidizing agent, about 0.1 toabout 95 wt-% oxidizing agent, about 1 to about 90 wt-% oxidizing agent,about 2.5 to about 60 wt-% oxidizing agent, about 5 to about 50 wt-%oxidizing agent, or about 10 to about 40 wt-% oxidizing agent.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 50 wt-% dispersing agent, about 0.1 toabout 40 wt-% dispersing agent, about 1 to about 30 wt-% dispersingagent, about 5 to about 30 wt-% dispersing agent, about 5 to about 20wt-% dispersing agent, or about 5 to about 15 wt-% dispersing agent. Theamount of dispersing agent is selected to ensure that only enoughdispersing agent to obtain a meta-stable solution after perhydrolysisand acidification. Beneficially according to the invention, the premixformulations do not contain sufficient dispersing agent to obtain a onephase premix solution.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 80 wt-% solvent, about 0.1 to about 40wt-% solvent, about 1 to about 30 wt-% solvent, about 5 to about 30 wt-%solvent, about 5 to about 20 wt-% solvent, or about 5 to about 15 wt-%solvent. 3 The level of solvent is selected to ensure the sufficientamount to solubilize the ester(s) of polyhydric alcohol in theconcentrated premix formulation. As one skilled in the art willascertain the amount of solvent required for such solubilization willvary depending upon the type and level of ester(s) in the premixcomposition.

In certain embodiments, the concentrated premix composition furtherincludes about 0.001 to about 90 wt-% water, about 0.1 to about 80 wt-%water, about 1 to about 75 wt-% water, about 5 to about 60 wt-% water,about 10 to about 50 wt-% water, or about 20 to about 40 wt-% water. Thepremix compositions can include any of these ranges or amounts,including those not modified by about.

The pH of the concentrated premix formulation according to the inventionis preferably between 2 and about 10, preferably between about 3 andabout 9, and more preferably between about 5 and about 7. Thereafter thepH of the premix formulation is combined with an a source of alkalinityto increase the pH to a pH greater than about 12, greater than about12.5, or greater than about 13 according to the invention.

Methods of Making Peracid Compositions

In some aspects methods for on-site generation of the peroxycarboxylicacid forming compositions and peroxycarboxylic acid using temperaturecontrols are disclosed. The methods include inputting a user-desired orsystem-controlled peroxycarboxylic acid forming composition orperoxycarboxylic acid formulation into a control software for on-sitegeneration, wherein the input formulation selects an individual or mixedperoxycarboxylic acid forming composition or peroxycarboxylic acid andcorresponding volume or mass for on-site generation.

The methods further comprise, consist of and/or consist essentially ofcombining at least one ester of a polyhydric alcohol and a C1 to C18carboxylic acid, a source of alkalinity and an oxidizing agent in areaction vessel of the system at a pH above at least 12. In someembodiments, the pH of the reaction mixture is greater than about 12. Inother embodiments, the reaction mixture is greater than about 12.5, orgreater than about 13. The methods include the use of a system that isinsensitive to environmental temperatures of the location of theapparatus and/or reagents as set forth according to the variousembodiments of the invention disclosed herein. The methods furthercomprise, consist of and/or consist essentially of generating aperoxycarboxylic acid forming composition or peroxycarboxylic acid.

In some embodiments a formulation user- or system-controlled input maybe put into a control software for an ABF system, wherein the inputformulation selects an individual or mixed peroxycarboxylic acid formingcomposition or peroxycarboxylic acid and the corresponding volume ormass of the chemistry for onsite generation. In further embodiments auser controls the input for the on-site chemistry generation. In furtherembodiments, a system-controlled input may include, for example, a CIPprocess, bottle washer, aseptic filler, vegetable wash or rinse sink,3^(rd) sink sanitizing sink, textile bleaching process and combinationsthereof.

In some embodiments, the user- or system-input selects either a singleor multiple reaction vessel mode for the peroxycarboxylic acid and/ormixed peroxycarboxylic acid or peroxycarboxylic acid forming compositiongeneration. As a result of the reaction vessel mode selected by theinput, the addition of the reaction reagents, including at least theesters, source of alkalinity and oxidizing agent, may be added inparallel or sequentially. The reagents can be combined in any suitablemanner according to the invention and mixed for an amount of timeeffective to form the desired percarboxylic acid forming composition orpercarboxylic acid concentration.

According to the invention, reagents may be added substantiallysimultaneously to a single reaction vessel, and mixed for an amount oftime effective to form the desired concentration. Alternatively,reagents may be added sequentially to a single reaction vessel orseparate reaction vessels. Still further, reagents may be combined fromseparate reaction vessels into an additional reaction vessel or areservoir (e.g. dilution tank).

According to an embodiment of the invention, the reagents are mixed inone or more reaction vessels for a period of time sufficient for theperhydrolysis reaction to occur. In some embodiments, the reagents aremixed for about 5 to about 30 minutes. In other embodiments, thereagents are mixed for about 10, about 15, about 20, or about 25minutes. The mixing may take place using a variety of mixing mechanisms,including for example, an impeller or a mechanical blade mixer, such asa mixer having a variable speed control motor to achieve homogeneousblending of reagents.

In additional preferred embodiments the mix order of reagents arecontrolled to produce a consistent output of peracid chemistry withoutany fouling (e.g. precipitation) of the reagents. In one aspect of theinvention, the source of alkalinity (e.g. sodium hydroxide or causticsoda) is combined with water (e.g. diluted) prior to the addition of theester source. As disclosed herein the ester source can further beprovided in an ester premix (e.g. ester/peroxide premix).

The concentration of reagents, in addition to mixing order, can furtherbe used to control the production of the percarboxylic acid composition.In a preferred embodiment, the concentration of the source of alkalinityis diluted to produce a consistent output of chemistry without anyfouling (e.g. precipitation) of the reagents. In one aspect theconcentrated alkaline solution (e.g. NaOH) is diluted with a watersource before the ester component is combined with the reagents.Although not intending to be limited according to any theory of theinvention and/or mechanism of action, the invention demonstratessuperior chemistry generation when a system delivers a source ofalkalinity (e.g. NaOH solution) that is no more than about 50%,preferably no more than about 40% on an actives basis before combiningwith the ester reagent to initiate the peracid production reaction.

According to preferred methods of making the peracid chemistry, anex-situ ABF generator system using an injection manifold to combine analkaline source, an ester precursor, a peroxygen source and optionallywater for production of a peroxy acid is used. Preferably the alkalinesource is caustic soda, wherein the caustic stream feeding the manifoldis a diluted source of alkalinity. In an aspect the caustic can bediluted within the manifold to the target concentration of less thanabout 50% by weight, preferably less than about 40%. In an additionalembodiment, the ester is added to the system downstream (e.g. after theaddition of the diluted NaOH solution).

In an embodiment, the extent of the ester perhydrolysis reaction ismeasured using one or more measurement devices. Suitable measurementdevices measures one or more reaction kinetics or system operations,including for example fluorescence, weight, flow, capacitive level, pH,oxidation reduction potential, pressure, temperature and combinationsthereof, as disclosed herein. According to an embodiment, themeasurement devices may be used to determine the need and/or timing toadd an acid or aqueous acidic solution to dilute the peroxycarboxylicacid forming composition to form the peroxycarboxylic acid composition.In some embodiments the addition of an acid or aqueous acidic solutiondecreases the pH of the reaction mixture from greater than about 12 to aneutralized pH of about 1.0 to about 8.0.

In an embodiment of the invention, the peroxycarboxylic acid formingcomposition is dispensed for use in a cleaning process. According to anembodiment, the peroxycarboxylic acid forming composition may begenerated in batches approximately at least about every 15 minutes,preferably about every 10 minutes, and more preferably about every 5minutes. An acid or aqueous acidic solution may be added to theperoxycarboxylic acid forming composition outside of the systemaccording to the invention.

In an embodiment of the invention, the peroxycarboxylic acid formingcomposition reaction goes to completion within less than about 30minutes, preferably within less than about 25 minutes, within less thanabout 20 minutes, within less than about 15 minutes, within less thanabout 10 minutes, and most preferably within less than about 5 minutes.

In a further embodiment of the invention, the peroxycarboxylic acidforming composition maintains a peracid concentration within about 10%of its final completion concentration for at least about 1 minute. Morepreferably, the peroxycarboxylic acid forming composition maintains aperacid concentration within about 10% of its final completionconcentration for at least about 2 minutes, for at least about 3minutes, for at least about 4 minutes, for at least 5 minutes, for atleast 10 minutes, for at least 15 minutes, and still more preferably forat least 20 minutes.

Preferably, the ABF system, including the reaction vessels, is cleanedbetween batches of peroxycarboxylic acid forming compositions. Rinsingof the ABF system is expected to have an impact on yield of theperoxycarboxylic acid forming compositions. According to an embodimentof the invention, the system is rinsed (e.g. feed pump lines flushed)with warm/hot water between batches, and/or at regularly schedulesintervals to comply with regulatory requirements (e.g. sanitizingregulations), as one skilled in the art shall ascertain.

A particularly suitable embodiment of the invention forms a mixedpercarboxylic acid composition by using more than one ester of apolyhydric alcohol and a C1 to C18 carboxylic acid as starting reagents.For example, in some embodiments, a mixed percarboxylic acid compositionincluding peracetic acid and peroctanoic acid is formed. To form thiscomposition, an ester of a polyhydric alcohol and a C1 carboxylic acidis combined with an ester of a polyhydric alcohol and a C8 carboxylicacid, a source of alkalinity, and an oxidizing agent. When forming amixed peracid composition, the order of addition can be varied dependingon the reaction conditions. For example, in some embodiments, all of thereagents can be combined and mixed in one step. Alternatively, in someembodiments, one of the esters can be added to a reaction vessel, withan oxidizing agent, and a source of alkalinity added sequentially. Thismixture can be allowed to react for an effective amount of time, priorto the second ester being added to the reaction mixture. Preparing themixed percarboxylic acid system in a stepwise manner also allows forcontrol of the reaction temperature. For example, by splitting theperhydrolysis reactions into two steps, the overall temperature of thereaction mixture is lower.

In some aspects of the invention, the order of addition and time forreaction can be varied according to the desired percarboxylic acidcomposition. That is, the reaction can be controlled so as to favor thereaction conditions for formation of each of the percarboxylic acidsindividually. For example, if it is known that one of the esters has akinetically slower perhydrolysis reaction rate, that ester can be addedto the reaction vessel first. After an amount of time sufficient tomaximize the percarboxylic acid formation of the first ester, the secondester with a kinetically faster perhydrolysis reaction rate can be addedto the reaction vessel.

According to additional aspects of the invention, the selected batchsize of a desired percarboxylic acid forming composition orpercarboxylic acid impacts the reaction kinetics. According to theinvention, a user- or system-inputted batch size (i.e. volume) to theABF system impacts the reaction kinetics. Although not intending to belimited to a particular theory, when generating various batch sizes withthe ABF system according to the invention, not all reactions arelinearly time-scaled, such that a larger batch size (i.e. hundreds ofgallons) may require a different timing sequence than a smaller batchsize (i.e. tens of gallons) depending on the reaction kinetics andvarious mixing parameters. The present invention accommodates thechanges in user- or system-inputted batch sizes, such that for differentvolumes of peracid compositions the time constants for its formulationwill vary.

In some aspects, the present disclosure provides methods for forming anantimicrobial and/or disinfecting composition. The methods includeproviding a mixed peroxycarboxylic acid forming composition. The mixedperoxycarboxylic acid forming composition includes: a first ester of apolyhydric alcohol and a C1 to C18 carboxylic acid, for example a C1 toC4 carboxylic acid; a second ester of a polyhydric alcohol and a C1 toC18 carboxylic acid, for example a C8 to C11 carboxylic acid; a sourceof alkalinity; and an oxidizing agent. After allowing the reactionmixture to react for a sufficient amount of time, a mixed percarboxylicacid composition is formed. The mixed peroxycarboxylic acid compositionis diluted with an acidic aqueous solution. In some embodiments, themixed peroxycarboxylic acid composition is diluted with an amount of anacidic aqueous solution effective to provide the diluted compositionwith a pH of about 1.0 to about 8.0.

In other aspects, the present disclosure provides methods for forming anantimicrobial and/or disinfecting composition including a singlepercarboxylic acid. The methods include providing a peroxycarboxylicacid forming composition. The composition includes: an ester of apolyhydric alcohol and a C1 to C18 carboxylic acid; a source ofalkalinity; and an oxidizing agent, wherein said composition has a pHgreater than 12. The peroxycarboxylic acid forming composition is thendiluted with an acidic aqueous solution. In some embodiments, thediluted acidic peroxycarboxylic acid composition has a pH of about 1.0to about 8.0.

Any acidic solution can be used to dilute the peroxycarboxylic acidcompositions. In an embodiment, the acidulant includes an inorganicacid. Suitable inorganic acids include, but are not limited to, sulfuricacid, sodium bisulfate, phosphoric acid, nitric acid, hydrochloric acid.In some embodiments, the acidulant includes an organic acid. Suitableorganic acids include, but are not limited to, methane sulfonic acid,ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid,xylene sulfonic acid, benzene sulfonic acid, formic acid, acetic acid,mono, di, or tri-halocarboyxlic acids, picolinic acid, dipicolinic acid,and mixtures thereof. In some embodiments, the compositions of thepresent invention are free or substantially free of a phosphorous basedacid.

Methods Employing Peracid Compositions

In some aspects, the present disclosure includes methods of using theperoxycarboxylic acid forming compositions disclosed herein. In someaspects, the methods of using the compositions employ a chemistry havinga pH of from about 0 to about 5 for various antimicrobial and/orbleaching applications. In other aspects, the methods of using thecompositions employ a chemistry having a pH of from about 5 to about 9for various antimicrobial and/or bleaching applications. In stillfurther aspects, the methods of using the compositions employ achemistry having a pH of from about 5 to about 14 for various bleachingapplications.

Peracid compositions generated according to the embodiments of theinvention may be used for a variety of user-identified biocidal and/oranti-microbial purposes. In some aspects, the on-site generated peracidcompositions may be employed for antimicrobial and/or bleaching methodsof use. In further aspects, the on-site generated peracid compositionsmay be employed for any sanitizing methods of use. For example, theinvention includes a method for reducing a microbial population, amethod for reducing the population of a microorganism on skin, a methodfor treating a disease of skin, a method for reducing an odor, or amethod for bleaching. These methods can operate on an object, surface,in a body or stream of water or a gas, or the like, by contacting theobject, surface, body, or stream with a peracid composition of theinvention. Contacting can include any of numerous methods for applying acomposition, such as spraying the composition, immersing the object inthe composition, foam or gel treating the object with the composition,wiping the composition or a combination thereof

In some aspects, a composition obtained according to the methods andapparatus of the present invention includes an amount of a peracidcomposition of the present invention effective for killing one or moreof the food-borne pathogenic bacteria associated with a food product,including, but not limited to, Salmonella typhimurium, Salmonellajaviana, Campylobacter jejuni, Listeria monocytogenes, and Escherichiacoli O157:H7, yeast, and mold. In some embodiments, the compositionsobtained according to the methods and apparatus of the present inventioninclude an amount of a peracid composition effective for killing one ormore of the pathogenic bacteria associated with a health care surfacesand environments including, but not limited to, Salmonella typhimurium,Staphylococcus aureus, Salmonella choleraesurus, Pseudomonas aeruginosa,Escherichia coli, mycobacteria, yeast, and mold. The compositionsobtained according to the methods and apparatus of the present inventionhave activity against a wide variety of microorganisms such as Grampositive (for example, Listeria monocytogenes or Staphylococcus aureus)and Gram negative (for example, Escherichia coli or Pseudomonasaeruginosa) bacteria, yeast, molds, bacterial spores, viruses, etc. Thecompositions obtained according to the methods and apparatus of thepresent invention, as described above, have activity against a widevariety of human pathogens. The present compositions obtained accordingto the methods and apparatus of the present invention can kill a widevariety of microorganisms on a food processing surface, on the surfaceof a food product, in water used for washing or processing of foodproduct, on a health care surface, in a health care environment or thelike.

The compositions obtained according to the methods and apparatus of theinvention can be used for a variety of domestic or industrialapplications, e.g., to reduce microbial or viral populations on asurface or object or in a body or stream of water. The compositions canbe applied in a variety of areas including kitchens, bathrooms,factories, hospitals, dental offices, restaurants, clean in placeapplications, laundry or textile applications and food plants, and canbe applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces can be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic.

Suitable soft surfaces include, for example, paper; filter media,hospital and surgical linens and garments; soft-surface medical orsurgical instruments and devices; and soft-surface packaging. Such softsurfaces can be made from a variety of materials including, for example,paper, fiber, woven or nonwoven fabric, soft plastics and elastomers.The compositions obtained according to the methods and apparatus of theinvention can also be applied to soft surfaces such as food and skin(e.g., a hand). The present compositions can be employed as a foaming ornonfoaming environmental sanitizer or disinfectant.

The peracid compositions obtained according to the methods and system ofthe present invention can be included in products such as sterilants,sanitizers, disinfectants, preservatives, deodorizers, antiseptics,fungicides, germicides, sporicides, virucides, detergents, bleaches,hard surface cleaners, hand soaps, waterless hand sanitizers, and pre-or post-surgical scrubs.

The compositions can also be used in veterinary products such asmammalian skin treatments or in products for sanitizing or disinfectinganimal enclosures, pens, watering stations, and veterinary treatmentareas such as inspection tables and operation rooms. The presentcompositions can be employed in an antimicrobial foot bath for livestockor people. The compositions can also be employed as an antimicrobialteat dip.

In some aspects, the compositions obtained according to the methods andapparatus of the present invention can be employed for reducing thepopulation of pathogenic microorganisms, such as pathogens of humans,animals, and the like. As one skilled in the art will ascertain, thereducing of pathogenic microorganism populations is particularlysuitable for healthcare and institutional applications of use. Thecompositions exhibit activity against pathogens including fungi, molds,bacteria, spores, and viruses, for example, S. aureus, E. coli,Streptococci, Legionella, Pseudomonas aeruginosa, mycobacteria,tuberculosis, phages, or the like. Such pathogens can cause a variety ofdiseases and disorders, including mastitis or other mammalian milkingdiseases, tuberculosis, and the like. The compositions of the presentinvention can reduce the population of microorganisms on skin or otherexternal or mucosal surfaces of an animal. In addition, the presentcompositions can kill pathogenic microorganisms that spread throughtransfer by water, air, or a surface substrate. The composition needonly be applied to the skin, other external or mucosal surfaces of ananimal water, air, or surface.

The peracid compositions obtained according to the methods and apparatusof the present invention can also be used on foods and plant species toreduce surface microbial populations; used at manufacturing orprocessing sites handling such foods and plant species; or used to treatprocess waters around such sites. For example, the compositions can beused on food transport lines (e.g., as belt sprays); boot and hand-washdip-pans; food storage facilities; anti-spoilage air circulationsystems; refrigeration and cooler equipment; beverage chillers andwarmers, blanchers, cutting boards, third sink areas, and meat chillersor scalding devices. The compositions of the invention can be used totreat produce transport waters such as those found in flumes, pipetransports, cutters, slicers, blanchers, retort systems, washers, andthe like. Particular foodstuffs that can be treated with compositions ofthe invention include, but are not limited to, eggs, meats, seeds,leaves, fruits and vegetables. Particular plant surfaces include bothharvested and growing leaves, roots, seeds, skins or shells, stems,stalks, tubers, corms, fruit, and the like. The compositions may also beused to treat animal carcasses to reduce both pathogenic andnon-pathogenic microbial levels.

The compositions can also be used to treat waste water where both itsantimicrobial function and its oxidant properties can be utilized. Asidefrom the microbial issues surrounding waste water, it is often rich inmalodorous compounds of reduced sulfur, nitrogen or phosphorous. Astrong oxidant such as the present invention converts these compoundsefficiently to their odor free derivatives e.g. the sulfates, phosphatesand amine oxides. These same properties are very useful in the pulp andpaper industry where the property of bleaching is also of great utility.

In some aspects, the compositions obtained according to the methods andapparatus of the present invention are useful in the cleaning orsanitizing of containers, processing facilities, or equipment in thefood service or food processing industries. The compositions haveparticular value for use on food packaging materials and equipment, andespecially for cold or hot aseptic packaging. Examples of processfacilities in which the composition of the invention can be employedinclude a milk line dairy, a continuous brewing system, food processinglines such as pumpable food systems and beverage lines, etc. Foodservice wares can be treated with an antimicrobial and/or disinfectedwith the composition of the invention. For example, the compositions canalso be used on or in ware wash machines, dishware, bottle washers,bottle chillers, warmers, third sink washers, cutting areas (e.g., waterknives, slicers, cutters and saws), egg washers or the like. Particulartreatable surfaces include, but are not limited to, packaging such ascartons, bottles, films and resins; dish ware such as glasses, plates,utensils, pots and pans; ware wash machines; exposed food preparationarea surfaces such as sinks, counters, tables, floors and walls;processing equipment such as tanks, vats, lines, pumps and hoses (e.g.,dairy processing equipment for processing milk, cheese, ice cream andother dairy products); and transportation vehicles. Containers includeglass bottles, PVC or polyolefin film sacks, cans, polyester, PEN or PETbottles of various volumes (100 ml to 2 liter, etc.), one gallon milkcontainers, paper board juice or milk containers, etc.

The compositions can also be used on or in other industrial equipmentand in other industrial process streams such as heaters, cooling towers,boilers, retort waters, rinse waters, aseptic packaging wash waters, andthe like. The compositions can be used to treat microbes and odors inrecreational waters such as in pools, spas, recreational flumes andwater slides, fountains, and the like. The composition can also be usedin treating microbes found in aqueous systems associated with petroleumor LP gas recovery or fermentation processes and pulp and paperprocesses and the like.

A filter containing peracid compositions of the present invention canreduce the population of microorganisms in air and liquids. Such afilter can remove water and air-borne pathogens such as Legionella.

The compositions obtained according to the methods and apparatus of thepresent invention can be employed for reducing the population ofmicrobes, fruit flies, or other insect larva on a drain or othersurface.

The compositions of the present invention can also be employed bydipping food processing equipment into the use solution, soaking theequipment for a time sufficient to sanitize or de-stain the equipment,and wiping or draining excess solution off the equipment. Thecompositions of the present invention may be further employed byspraying or wiping food processing surfaces with the use solution,keeping the surfaces wet for a time sufficient to sanitize the surfaces,and removing excess solution by wiping, draining vertically, vacuuming,etc.

The compositions obtained according to the methods and system of thepresent invention may also be used in a method of sanitizing hardsurfaces such as institutional type equipment, utensils, dishes, healthcare equipment or tools, and other hard surfaces.

The compositions of the present invention can also be used for laundryor textile applications. The compositions can be employed by rinsinglaundry or textile surfaces with the use solution, keeping the surfaceswet for a sufficient time to wash, de-stain, sanitize, bleach and/orrinse the surface.

The peracid compositions can be applied to microbes or to soiled orcleaned surfaces using a variety of methods. These methods can operateon an object, surface, in a body or stream of water or a gas, or thelike, by contacting the object, surface, body, or stream with acomposition of the invention. Contacting can include any of numerousmethods for applying a composition, such as spraying the composition,immersing the object in the composition, rinsing the composition, foamor gel treating the object with the composition, applying with a wipesystem or a combination thereof.

A concentrate or use concentration of a peracid composition obtainedaccording to the methods and apparatus of the present invention can beapplied to or brought into contact with an object by any conventionalmethod or apparatus for applying an antimicrobial or cleaningcomposition to an object. For example, the object can be wiped with,sprayed with, foamed on, and/or immersed in the composition, or a usesolution made from the composition. The compositions can be sprayed,foamed, or wiped onto a surface; the composition can be caused to flowover the surface, or the surface can be dipped into the composition.Contacting can be manual or by machine. Food processing surfaces, foodproducts, food processing or transport waters, and the like can betreated with liquid, foam, gel, aerosol, gas, wax, solid, or powderedperacid compositions according to the invention, or solutions containingthese compositions.

Other hard surface cleaning applications for the compositions includeclean-in-place systems (CIP), clean-out-of-place systems (COP),washer-decontaminators, sterilizers, textile laundry machines, ultra andnano-filtration systems and indoor air filters. COP systems can includereadily accessible systems including wash tanks, soaking vessels, mopbuckets, holding tanks, scrub sinks, vehicle parts washers,non-continuous batch washers and systems, and the like. CIP systemsinclude the internal components of tanks, lines, pumps and other processequipment used for processing typically liquid product streams such asbeverages, milk, juices.

A method of sanitizing substantially fixed in-place process facilitiesincludes the following steps. A composition in accordance with variousembodiments of the invention is introduced into the process facilitiesat a temperature in the range of about 4° C. to 60° C. Afterintroduction of the composition, the solution is held in a container orcirculated throughout the system for a time sufficient to sanitize theprocess facilities (e.g., to kill undesirable microorganisms). After thesurfaces have been sanitized by means of the present compositions, thesolution is drained. Upon completion of the sanitizing step, the systemoptionally may be rinsed with other materials such as potable water. Thecompositions can be circulated through the process facilities for 10minutes or less.

The present methods can include delivering the present composition viaair delivery to the clean-in-place or other surfaces such as thoseinside pipes and tanks. This method of air delivery can reduce thevolume of solution required.

Methods for Contacting a Food Product

In some aspects, the present invention provides methods for contacting afood product with compositions according to the invention employing anymethod or apparatus suitable for applying such compositions. Forexample, in some embodiments, the food product is contacted by thecompositions with a spray of the compositions, by immersion in thecompositions, by foam or gel treating with the compositions. Contactwith a spray, a foam, a gel, or by immersion can be accomplished by avariety of methods known to those of skill in the art for applyingantimicrobial agents to food. Contacting the food product can occur inany location in which the food product might be found, such as field,processing site or plant, vehicle, warehouse, store, restaurant, orhome. These same methods can also be adapted to apply the compositionsof the present invention to other objects.

The present methods require a certain minimal contact time of thecompositions with food product for occurrence of significantantimicrobial effect. The contact time can vary with concentration ofthe use compositions, method of applying the use compositions,temperature of the use compositions, amount of soil on the food product,number of microorganisms on the food product, type of antimicrobialagent, or the like. The exposure time can be at least about 5 to about15 seconds. In some embodiments, the exposure time is about 15 to about30 seconds. In other embodiments, the exposure time is at least about 30seconds.

In some embodiments, the method for washing a food product employs apressure spray including compositions of the present invention. Duringapplication of the spray solution on the food product, the surface ofthe food product can be moved with mechanical action, e.g., agitated,rubbed, brushed, etc. Agitation can be by physical scrubbing of the foodproduct, through the action of the spray solution under pressure,through sonication, or by other methods. Agitation increases theefficacy of the spray solution in killing micro-organisms, perhaps dueto better exposure of the solution into the crevasses or small coloniescontaining the micro-organisms. The spray solution, before application,can also be heated to a temperature of about 15 to 20° C., for example,about 20 to 60° C. to increase efficacy. The spray stabilizedcompositions can be left on the food product for a sufficient amount oftime to suitably reduce the population of microorganisms, and thenrinsed, drained, or evaporated off the food product.

Application of the material by spray can be accomplished using a manualspray wand application, an automatic spray of food product moving alonga production line using multiple spray heads to ensure complete contact,or other spray apparatus. One automatic spray application involves theuse of a spray booth. The spray booth substantially confines the sprayedcompositions to within the booth. The production line moves the foodproduct through the entryway into the spray booth in which the foodproduct is sprayed on all its exterior surfaces with sprays within thebooth. After a complete coverage of the material and drainage of thematerial from the food product within the booth, the food product canthen exit the booth. The spray booth can include steam jets that can beused to apply the stabilized compounds of the invention. These steamjets can be used in combination with cooling water to ensure that thetreatment reaching the food product surface is less than 65° C., e.g.,less than 60° C. The temperature of the spray on the food product isimportant to ensure that the food product is not substantially altered(cooked) by the temperature of the spray. The spray pattern can bevirtually any useful spray pattern.

Immersing a food product in the liquid compositions of the presentinvention can be accomplished by any of a variety of methods known tothose of skill in the art. For example, the food product can be placedinto a tank or bath containing the compositions. Alternatively, the foodproduct can be transported or processed in a flume of the compositions.The washing solution can be agitated to increase the efficacy of thesolution and the speed at which the solution reduces micro-organismsaccompanying the food product. Agitation can be obtained by conventionalmethods, including ultrasonics, aeration by bubbling air through thesolution, by mechanical methods, such as strainers, paddles, brushes,pump driven liquid jets, or by combinations of these methods. Thewashing solution can be heated to increase the efficacy of the solutionin killing micro-organisms. After the food product has been immersed fora time sufficient for the desired antimicrobial effect, the food productcan be removed from the bath or flume and the compositions can berinsed, drained, or evaporated off the food product.

In other embodiments, a food product can be treated with a foamingversion of the compositions of the present invention. The foam can beprepared by mixing foaming surfactants with the washing solution at timeof use. The foaming surfactants can be nonionic, anionic or cationic innature. Examples of useful surfactant types include, but are not limitedto the following: alcohol ethoxylates, alcohol ethoxylate carboxylate,amine oxides, alkyl sulfates, alkyl ether sulfate, sulfonates,including, for example, alkyl aryl sulfonates, quaternary ammoniumcompounds, alkyl sarcosines, betaines and alkyl amides. The foamingsurfactant is typically mixed at time of use with the washing solution.Use solution levels of the foaming agents is from about 50 ppm to about2.0 wt-%. At time of use, compressed air can be injected into themixture, then applied to the food product surface through a foamapplication device such as a tank foamer or an aspirated wall mountedfoamer.

In some embodiments, a food product can be treated with a thickened orgelled version of the compositions of the present invention. In thethickened or gelled state the washing solution remains in contact withthe food product surface for longer periods of time, thus increasing theantimicrobial efficacy. The thickened or gelled solution will alsoadhere to vertical surfaces. The compositions can be thickened or gelledusing existing technologies such as: xanthan gum, polymeric thickeners,cellulose thickeners, or the like. Rod micelle forming systems such asamine oxides and anionic counter ions could also be used. The thickenersor gel forming agents can be used either in the concentrated product ormixing with the washing solution, at time of use. Typical use levels ofthickeners or gel agents range from about 100 ppm to about 10 wt-%.

Methods for Beverage, Food, and Pharmaceutical Processing

The compositions of the present invention can be used in the manufactureof beverage, food, and pharmaceutical materials including fruit juice,dairy products, malt beverages, soybean-based products, yogurts, babyfoods, bottled water products, teas, cough medicines, drugs, and softdrinks. The compositions of the present invention can be used tosanitize, disinfect, act as a sporicide for, or sterilize bottles,pumps, lines, tanks and mixing equipment used in the manufacture of suchbeverages. Further, the compositions of the present invention can beused in aseptic, cold filling operations in which the interior of thefood, beverage, or pharmaceutical container is sanitized or sterilizedprior to filling. In such operations, a container can be contacted withthe compositions, typically using a spray, dipping, or filling device tointimately contact the inside of the container with the compositions,for a sufficient period of time to reduce microorganism populationswithin the container. The container can then be emptied of the amount ofsanitizer or sterilant used. After emptying, the container can be rinsedwith potable water or sterilized water and again emptied. After rinsing,the container can be filled with the beverage, food, or pharmaceutical.The container can then be sealed, capped or closed and then packed forshipment for ultimate sale. The sealed container can be autoclaved orretorted for added microorganism kill.

In food, beverage, or pharmaceutical manufacturing, fungalmicroorganisms of the genus Chaetomium or Arthrinium, and spores orbacteria of the genus Bacillus spp. can be a significant problem inbottling processes, particularly in cold aseptic bottling processes. Thecompositions of the present invention can be used for the purpose ofcontrolling or substantially reducing (by more than a 5 log₁₀ reduction)the number of Chaetomium or Arthrinium or Bacillus microorganisms inbeverage or food or pharmaceutical bottling lines using cold asepticbottling techniques.

In such techniques, metallic, aluminum or steel cans can be filled,glass bottles or containers can be filled, or plastic (PET or PBT orPEN) bottles, and the like can be filled using cold aseptic fillingtechniques. In such processes, the compositions of the invention can beused to sanitize the interior of beverage containers prior to fillingwith the carbonated (or noncarbonated) beverage. Typical carbonatedbeverages in this application include, but are not limited to, colabeverages, fruit beverages, ginger ale beverages, root beer beverages,iced tea beverages which may be non-carbonated, and other commonbeverages considered soft drinks. The compositions of the invention canbe used to sanitize both the tanks, lines, pumps, and other equipmentused for the manufacture and storage of the soft drink material and alsoused in the bottling or containers for the beverages. In an embodiment,the compositions are useful for killing both bacterial and fungalmicroorganisms that can be present on the surfaces of the productionequipment and beverage containers.

Methods for Industrial Processing

In some aspects, the invention includes methods of using theperoxycarboxylic acid forming compositions and/or peroxycarboxylic acidsto prevent biological fouling in various industrial processes andindustries, including oil and gas operations, to control microorganismgrowth, eliminate microbial contamination, limit or prevent biologicalfouling in liquid systems, process waters or on the surfaces ofequipment that come in contact with such liquid systems. As referred toherein, microbial contamination can occur in various industrial liquidsystems including, but not limited to, air-borne contamination, watermake-up, process leaks and improperly cleaned equipment. In anotheraspect, the peroxycarboxylic acid forming compositions and/orperoxycarboxylic acids are used to control the growth of microorganismsin water used in various oil and gas operations. In a further aspect,the compositions are suitable for incorporating into fracturing fluidsto control or eliminate microorganisms.

For the various industrial processes disclosed herein, “liquid system”refers to flood waters or an environment within at least one artificialartifact, containing a substantial amount of liquid that is capable ofundergoing biological fouling, it includes but is not limited toindustrial liquid systems, industrial water systems, liquid processstreams, industrial liquid process streams, industrial process watersystems, process water applications, process waters, utility waters,water used in manufacturing, water used in industrial services, aqueousliquid streams, liquid streams containing two or more liquid phases, andany combination thereof.

In at least one embodiment this technology would be applicable to anyprocess or utility liquid system where microorganisms are known to growand are an issue, and biocides are added. Examples of some industrialprocess water systems where the method of this invention could beapplied are in process water applications (flume water, shower water,washers, thermal processing waters, brewing, fermentation, CIP (clean inplace), hard surface sanitization, etc.), Ethanol/Bio-fuels processwaters, pretreatment and utility waters (membrane systems, ion-exchangebeds), water used in the process/manufacture of paper, ceiling tiles,fiber board, microelectronics, E-coat or electro depositionapplications, process cleaning, oil exploration and energy services(completion and work over fluids, drilling additive fluids, fracturingfluids, flood waters, etc.; oil fields—oil and gas wells/flow line,water systems, gas systems, etc.), and in particular water systems wherethe installed process equipment exhibits lowered compatibility tohalogenated biocides.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures, embodiments, claims, and examples described herein.Such equivalents are considered to be within the scope of this inventionand covered by the claims appended hereto. The contents of allreferences, patents, and patent applications cited throughout thisapplication are hereby incorporated by reference. The invention isfurther illustrated by the following examples, which should not beconstrued as further limiting.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

A single peracid chemistry (POOA) was generated using an ABF generatoraccording to an embodiment of the invention using the reagents set forthin Table 1A.

TABLE 1A Reagent Formula Amt (%) ABF POOA Glycerol Octanoate 14.67% H₂O₂35% 19.42% Water 49.44% NaOH 50% 16.47%

POOA production rates were generated as a function of reagents andgenerator temperatures. A continuous ABF generator was used wherein boththe reagent and reaction vessels temperature were controlled with aheating/cooling water bath as set forth in Table 1B. The resultsdemonstrate the POOA production as a function of time.

TABLE 1B 5° C. Rxn 20° C. Rxn 30° C. Rxn 40° C. Rxn % % % % POOA POOAPOOA POOA time 5° C. time 20° C. Time 30° C. time 40° C. 10 2.55 1 2.071 1 5.19 20 3.45 5 3.89 3 4.56 3 6.23 30 3.90 10 4.77 5 5.24 5 6.06 404.20 15 5.46 10 6.35 7 5.36 50 4.20 20 5.83 15 6.57 10 5.40 60 4.50 256.30 20 6.52 15 3.38 70 4.72 30 6.67 30 6.29 20 3.82 40 6.77 45 5.60 506.73 90 4.36 70 6.61 90 6.36 160 5.66

The results are shown in FIG. 3 (graphical representation of POOAconcentration over time at various reaction temperatures). The graphconfirms that under different environmental temperatures theconcentration of available peracid is widely variable. The variabilitydepends upon the temperature of the generator and temperature of thereactants (e.g. raw starting materials) and of the time point at whichthe reaction mixture would be used. These results demonstrate theimportance of mechanisms for controlling the ex-situ peracid reactiontemperature of the reaction vessel or reaction manifold (i.e. regardlessof whether batch and/or continuous generation apparatus and/or methodsare used according to the invention). The control of temperature impactsthe kinetics of the reaction and therefore can be critical toconsistency of peracid output according to the invention.

Example 2

Methods of thermal control were analyzed. The reaction rates of a singleperacid chemistry (POOA) generated using an ABF generator according toan embodiment of the invention were analyzed. The reagents set forth inTable 2A were used to generate POOA. The test utilized reactants thatwere stored at either 5° C. or 40° C. (as further shown in Table 2B) torepresent the changes in (and ranges of) temperatures one skilled in theart may expect in practice.

TABLE 2A Reagent Formula Amt (%) ABF POOA Glycerol Octanoate 9.83% H₂O₂35% 13.02% Water (21° C.) 65.90% NaOH 50% 11.21%

The test used a jacket to cover the reaction vessel of the ABF generatorto control the temperature of the reagents. In the testing a batch ABFgenerator was employed (however the same tested methods can be employedfor a continuous generator as disclosed pursuant to the invention). Thetemperature was controlled to 20° C. (˜69° F.). In this reaction theglycerol octanoate, peroxide and water reagents (e.g. raw startingmaterials) were added to the reaction vessel first. Once thoseingredients were combined the 50% NaOH was added. For purposes oftesting this reaction scheme was utilized as a result of the addition ofNaOH both initiating the reaction and causing a large exothermic effect.Both temperature and resultant peracid were monitored in this reaction.

POOA production rates and temperature were monitored as a function oftime with reaction vessel temperatures controlled to 20° C., wherein thereagents were stored at either 5° C. or 40° C. The results are shown inTable 2B.

TABLE 2B temp with temp with 5° C. 40° C. POOA POOA time (mm) reagentsreagents @ 5° C. @ 40° C. 0 69 84 0 0 1 80 84 0.73 0.95 3 72 73 1.361.58 5 70 71 1.69 1.90 10 69 69 2.28 2.44 20 69 69 2.80 3.04 30 69 693.22 3.50 45 69 69 3.72 3.98 60 69 69 4.02 4.24 90 69 69 4.30 4.23 12069 69 4.03 4.00 180 69 69 3.57

The results are further shown in the graph of FIG. 4. The identifiedtime period from approximately 50 minutes to 120 minutes (shown in theboxed area of the graph) outlines where the 2 separate reaction mixtures(one with reagents starting at 5° C. and one with reagents starting at40° C.) achieved maximum percentage POOA generation. These resultsdemonstrate the ability to use temperature control as a means of drivingtoward consistency in the chemistry output of an ex-situ peracidgenerator without regard to environmental temperatures.

This example required increased time to achieve maximum generation ofthe peracid chemistry, notably about 50 minutes to achieve the +/−10%max target for peracid generation. However, as one skilled in the art ofchemical reaction kinetics will ascertain, to decrease the time periodfor achieving maximum peracid generation the temperature of the reactionvessel and/or reaction manifold can be increased.

Example 3

Additional methods of thermal control were analyzed. The thermal controlscheme outlined in Example 2 may add cost and/or complexity to an ABFsystem. As a result, improvements to the various methods for includingtemperature control for a reaction vessel and/or reaction manifold wereanalyzed. An alternative was evaluated—heating one or more of the rawstarting materials (i.e. reagents) for the ex-situ peracid composition.The heating of reagents as opposed to the reaction vessel and/orreaction manifold was evaluated as a means to control the reactionkinetics in the ABF system.

In this analysis water was selected as the raw starting material thatwas temperature controlled. Water was selected based on the fact thatwater tends to be the most abundant reagent in many peracid recipesaccording to the invention. In addition, the heating of water can beeasily and inexpensively achieved as one skilled in the art willappreciate.

The reagents set forth in Table 3A were used to generate POOA.

TABLE 3A Reagent Formula Amt (%) ABF POOA Glycerol Octanoate 9.83% H₂O₂35% 13.02% Water 65.90% NaOH 50% 11.21%

Table 3B shows the POOA production rates and temperature as a functionof time with reagent temperatures controlled to variable temperatures−5° C. and 40° C., as opposed to temperature control of the reactionvessel and/or reaction manifold. The results are shown in Table 3B.

TABLE 3B POOA POOA Rxn Temp Rxn Temp 5° C. 40° C. 5° C. 40° C. time(min) reagents reagents reagents reagents 0 0 0 89 94 1 1.26 1.65 109117 3 2.30 2.68 106 112 5 2.82 3.16 103 108 10 3.56 3.65 96 100 15 3.703.87 85 94 20 3.83 3.83 87 89 30 3.92 3.76 80 81 45 3.90 3.63 74 75 603.80 3.52 72 72 90 3.62 72

The results are further shown in the graph of FIG. 5. The resultsdemonstrate the potential to use a heated water source to producereaction kinetic rates in in ex-situ peracid generator through the useof a heated water source with no other temperature control in the ABFsystem.

Example 4

Examples 1-3 highlight the importance of using warm water to controlreaction rate and stability. Example 4 in contrast outlines an situationwhere a cooler temperature is preferred to both control reaction rateand stabilize the peracid that is formed.

The reagents set forth in Table 4A were used to generate POAA in a benchtop experiment@ambient environmental temperatures ˜70° F. (˜21° C.)

TABLE 4A Reagent Formula Amt (%) ABF POAA Triacetin 6.0% H₂O₂ 50% 11.7%Water 79.8% NaOH 50% 3.0%

Table 4B shows the POAA production rates and temperature as a functionof time using water in the reaction that was preheated to 104 F (40 C).

TABLE 4B Rxn Temp. (degrees Time (min) F.) 104° F. water % POAA 0 96 1110 2.41 2 112 2.25 3 113 1.99 4 113 1.77 5 113 1.58 10 112 0.83Table 4C in contrast show the same reaction scheme using 38 F (˜3.3 C)water

TABLE 4C Rxn Temp. (degrees time (min) F.) 38° F. water POAA 0 46 1 562.22 3 58 2.49 5 60 2.52 10 64 2.44 15 67 2.36

The key difference in these reactions is not in yield, as bothcompositions develop a maximum concentration of ˜2.5% POAA. The criticaldifference comes down to the stability of the resultant reaction and theability to maintain a +/−10% max POAA window with the use of cooler thanambient water in this reaction scheme.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims.

1. A temperature controlled adjustable biocide formulator or generatorsystem for on-site peroxycarboxylic acid forming composition generationcomprising: an apparatus for producing a peroxycarboxylic acid formingcomposition that is insensitive to environmental temperatures of thelocation of the apparatus and/or one or more reagents, comprising areaction vessel and/or reaction manifold, a series of feed pumps, anoutlet for dosing the peroxycarboxylic acid forming composition fromsaid reaction vessel and/or reaction manifold, and a controller for auser- or system-inputted selection device; a temperature controlledmechanism for maintaining a controlled temperature of said reactionvessel and/or reaction manifold and/or the one or more reagents, whereinsaid reagents comprise at least one ester of a polyhydric alcohol and aC1 to C18 carboxylic acid, a source of alkalinity, and an oxidizingagent, at an alkaline pH.
 2. The system according to claim 1, whereinsaid controlled temperature is maintained between about 4.4° C. to about60° C.
 3. The system according to claim 1, wherein the source ofalkalinity is sodium hydroxide, and wherein said sodium hydroxide isprovided to said reaction vessel and/or reaction manifold prior to theaddition of said ester in a diluted solution.
 4. The system according toclaim 1, further comprising at least one measurement device, whereinsaid measurement device measures one or more reaction kinetics or systemoperations for said peroxycarboxylic acid forming composition generationselected from the group consisting of fluorescence, weight, flow,capacitive level, pH, oxidation reduction potential, pressure,temperature and combinations thereof.
 5. The system according to claim1, wherein the peroxycarboxylic acid forming composition reaction goesto completion within less than about 30 minutes and maintains a peracidconcentration within about 10% of its final completion concentration forat least about 1 minute.
 6. The system according to claim 1, whereinsaid temperature control mechanism is selected from the group consistingof external heating or cooling of the reaction vessel and/or reactionmanifold, internal heating of one or more of the reagents within thereaction vessel and/or reaction manifold, preheating one or more of thereagents, and combinations of the same.
 7. The system according to claim6, wherein said reaction vessel and/or reaction manifold is a flowthrough reactor or a batch reactor and the internal heating of the oneor more reagents within the reaction vessel and/or reaction manifold, orthe preheating of the one or more reagents is water.
 8. The systemaccording to claim 1, wherein said apparatus further comprises areservoir in fluid connection with said reaction vessel and/or reactionmanifold outlet to mix or store said peroxycarboxylic acid formingcompositions from said reaction vessel and/or reaction manifold.
 9. Thesystem according to claim 8, further comprising an additional feed pumpproviding an acid or acidic aqueous solution in fluid communication withsaid reservoir, wherein said acid or acidic aqueous solution dilutessaid peroxycarboxylic acid forming composition to form aperoxycarboxylic acid having a pH of about 0.1 to about 8.0, wherein theneutralization with the acid or aqueous acidic solution takes place whenthe concentration of the peroxycarboxylic acid is within about 10% ofits final concentration.
 10. The system according to claim 1, furthercomprising a control software for operating said apparatus to generate auser- or system-inputted peroxycarboxylic acid forming composition anddesired volume of said peroxycarboxylic acid forming composition foron-site generation, and wherein said control software determines thetiming of feeding said raw materials to said reaction vessel and/orreaction manifold, mixing and reaction time required for production ofsaid user- or system-inputted peroxycarboxylic acid forming compositionand desired volume.
 11. The system according to claim 1, furthercomprising a data output means for sharing information related to saidperoxycarboxylic acid forming composition formulation, peroxycarboxylicacid forming composition consumption or usage, additionalperoxycarboxylic acid forming composition production-related data orcombinations of the same.
 12. The system according to claim 1, whereinsaid feed pumps are in fluid connection with said reaction vessel and/orreaction manifold and supply one or more reagents to produce saidperoxycarboxylic acid forming composition in said reaction vessel and/orreaction manifold.
 13. The system according to claim 1, wherein saidreaction vessel and/or reaction manifold is in fluid connection withsaid outlet to dispense said peroxycarboxylic acid forming composition.14. The system according to claim 2, wherein said controlled temperatureis adjusted to between about 21° C. to about 49° C.